Deprecated: The each() function is deprecated. This message will be suppressed on further calls in /home/zhenxiangba/zhenxiangba.com/public_html/phproxy-improved-master/index.php on line 456
EP4421131A1 - Polymeric dyes - Google Patents
[go: Go Back, main page]

EP4421131A1 - Polymeric dyes - Google Patents

Polymeric dyes Download PDF

Info

Publication number
EP4421131A1
EP4421131A1 EP23158134.9A EP23158134A EP4421131A1 EP 4421131 A1 EP4421131 A1 EP 4421131A1 EP 23158134 A EP23158134 A EP 23158134A EP 4421131 A1 EP4421131 A1 EP 4421131A1
Authority
EP
European Patent Office
Prior art keywords
monomer
polymeric dye
reactive
group
ink composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP23158134.9A
Other languages
German (de)
French (fr)
Inventor
Camille CHATARD
Alain GRAILLOT
Guillaume FALCO
Frederic BODINO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dover Europe SARL
Original Assignee
Dover Europe SARL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dover Europe SARL filed Critical Dover Europe SARL
Priority to EP23158134.9A priority Critical patent/EP4421131A1/en
Priority to AU2024225279A priority patent/AU2024225279A1/en
Priority to PCT/EP2024/054622 priority patent/WO2024175761A1/en
Priority to EP24706454.6A priority patent/EP4669709A1/en
Priority to KR1020257027987A priority patent/KR20250151639A/en
Priority to JP2025549579A priority patent/JP2026507071A/en
Priority to CN202480014588.8A priority patent/CN120917101A/en
Publication of EP4421131A1 publication Critical patent/EP4421131A1/en
Priority to MX2025009889A priority patent/MX2025009889A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/023—Emulsion inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention relates to a polymeric dye as well as to related ink compositions, products, and processes.
  • the present invention relates to a polymeric dye resulting from the polymerization of polymerizable monomers bearing a polymerizable function, such as acrylate, methacrylate, acrylamide, or methacrylamide, and a chromophore function.
  • a polymerizable function such as acrylate, methacrylate, acrylamide, or methacrylamide
  • the ink is typically ejected through a component of a printhead (e.g., an array of nozzles) onto a substrate.
  • a component of a printhead e.g., an array of nozzles
  • Many solvent-soluble dyes currently used in the inkjet printing have been identified as materials hazardous for human and environment with long-term compliance issues.
  • These dyes are typically coordinated to heavy metals, which could contribute to the toxicity of such dyes.
  • Organic part contains diazo function, and the metallic cation is trivalent chromium ion.
  • colored dyes such as blue and red dyes, also include metallic cations, like copper, cobalt and iron.
  • CMR chemicals as dyes
  • sensitive markets such as from food, pharmaceutical, and cosmetic industries.
  • Colored polymeric dyes are known in the art such as for example, from US7732509B2 , US7273897B2 , WO03089533 , WO9961533 , DE19651689 , CN108071023B and CN101787222A .
  • such documents mainly disclose water-soluble polymeric dyes.
  • the Applicant has faced the problem of developing organic solvent-soluble polymeric dyes that do not contain heavy metals.
  • the solution comprises a method for synthetizing a polymeric dye comprising the steps of:
  • the polymerizable monomer dye can be easily prepared by reaction of one reactive function, such as a hydroxyl group, an amine group, or a carboxyl group, of a dye with a reactive function of a polymerizable monomer, such as an acyl chloride or an anhydride or an ester or a carboxylic acid, or a hydroxyl group, or an amine group.
  • one reactive function such as a hydroxyl group, an amine group, or a carboxyl group
  • a dye with a reactive function of a polymerizable monomer, such as an acyl chloride or an anhydride or an ester or a carboxylic acid, or a hydroxyl group, or an amine group.
  • the copolymerization of at least one polymerizable monomer dye with polymerizable monomers can be easily conducted in the presence of a suitable initiator in a suitable solvent.
  • the Applicant has found that by copolymerizing two or more polymerizable monomer dyes having different chromophores, a wide range of polymeric dyes having different colors (black, cyan, magenta, yellow, blue, red, and green) can be obtained.
  • the present invention relates to a polymeric dye and to the preparation process thereof.
  • Such a polymeric dye can be used as a dye in a continuous inkjet (CIJ) printing process or a drop-on-demand (DOD) printing process (e.g., a thermal inkjet (TIJ) printing process) or a hot melt (HM) inkjet printing process.
  • CIJ continuous inkjet
  • DOD drop-on-demand
  • TIJ thermal inkjet
  • HM hot melt
  • the polymeric dye of the present invention can form an ink composition without including any toxic metallic cation and with fair fastness, while still possessing excellent stability, printability, solubility in organic solvent, and adhesion to a variety of substrates.
  • the present invention relates to an ink composition that includes the polymeric dye of the present invention, and an organic solvent.
  • the composition can be a solution.
  • the polymeric dye of the present invention can be in an amount of from about 1 % to about 70% by weight, preferably from 3% to 50% by weight, with respect to the weight of the ink composition.
  • the present invention relates to a product that includes a substrate (e.g., a cardboard, a glass, a metal, or a film) and a solid ink defining an image on the substrate, in which the solid ink includes the ink composition described herein.
  • a substrate e.g., a cardboard, a glass, a metal, or a film
  • the solid ink includes the ink composition described herein.
  • the present invention relates to a printing process that includes ejecting the ink composition described herein from a printhead in an inkjet printer onto a substrate to form an image.
  • Figures 1 to 6 shows the results of the printing test as described in example 10 immediately after printing ( Figure 1 ) and after 10, 18, 28, 35, and 50 hours of lightfastness aging ( Figures 2-6 , respectively).
  • the polymeric dye according to the present invention is a co-polymer comprising the monomer repeating units having the following formulas (I) and (II): wherein M1 and M2, equal or different each other, are reactive monomers, and C1 and C2, different each other, are chromophore units.
  • the polymeric dye according to the present invention can optionally comprises the monomer repeating units having the following formulas (III) and (IV): wherein M3 and M4, equal or different each other, are reactive monomers, and C3 is a chromophore unit different from C1 and C2.
  • the polymeric dye can optionally comprise the monomer repeating unit having the following formulas (V): wherein M5 is a reactive monomer, and C4 is a chromophore unit different from C1-C3.
  • M1 to M5 are selected from the group consisting of acrylic acid monomer, methacrylic acid monomer, acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, vinyl alcohol monomer, vinyl amine monomer, and the like.
  • any one of C1-C4 can be a blue chromophore unit derived from a commercial dye selected from the group consisting of:
  • any one of C1-C4 can be a red chromophore unit derived from a commercial dye selected from the group consisting of:
  • any one of C1-C4 can be a green chromophore unit derived from a commercial dye selected from the group consisting of:
  • any one of C1-C4 can be a chromophore unit derived from a commercial dye selected from the group consisting of:
  • the preferred commercial dyes are those including at least one reactive function, such as a hydroxyl group, an amine group, or a carboxyl group, able to react with a reactive function of a polymerizable monomer.
  • commercial dyes not having any reactive function can be used for the scope of the present invention by derivatization to include a reactive function.
  • the polymeric dye according to the present invention can be a block copolymer, a random copolymer, or a graft copolymer. In a preferred embodiment, the polymeric dye according to the present invention is a random copolymer.
  • the polymeric dye according to the present invention can have a weight average molecular weight of at least about 1,000 Da (e.g., at least about 2,000 Da, at least about 5,000 Da, at least about 7,500 Da, at least about 10,000 Da, at least about 12,500 Da, at least about 15,000 Da, at least about 17,500 Da, or at least about 20,000 Da) to at most about 120,000 Da (e.g., at most about 115,000 Da, at most about 110,000 Da, at most about 105,000 Da, at most about 100,000 Da, at most about 95,000 Da, or at most about 90,000 Da).
  • a weight average molecular weight of at least about 1,000 Da (e.g., at least about 2,000 Da, at least about 5,000 Da, at least about 7,500 Da, at least about 10,000 Da, at least about 12,500 Da, at least about 15,000 Da, at least about 17,500 Da, or at least about 20,000 Da) to at most about 120,000 Da (e.g., at most about 115,000 Da, at most about 110,000 Da, at most about 105,000 Da
  • the polymeric dye according to the present invention can comprise an amount of any one of the monomer repeating units having the formulas (I) to (V) of from at least about 5% (e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 80% (e.g., at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight with respect to the weight average molecular weight of the polymeric dye.
  • at least about 5% e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%
  • at most about 80% e.g., at most about 75%, at most about 70%, at most about 65%, at most about
  • the polymeric dye according to the present invention comprises an amount of any one of the monomer repeating units having the formulas (I), (II) and (IV) of from at least about 5% (e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 80% (e.g., at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight with respect to the weight average molecular weight of the polymeric dye.
  • at least about 5% e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%
  • at most about 80% e.g., at most about 75%, at most about 70%, at most about 65%,
  • the polymeric dye according to the present invention comprises a total amount of monomer repeating units having the formulas (I) and (II) of from at least about 10% (e.g., at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight with respect to the weight average molecular weight polymeric dye, the remaining amount being represented by monomer repeating units having the formula (IV), and optionally by monomer repeating units having the formulas (III) and (V).
  • a total amount of monomer repeating units having the formulas (I) and (II) of from at least about 10% (e.g., at least about 15%, at least about 20%, at least about 25%, at least about 30%
  • the polymeric dye according to the present invention can have a relatively high solubility in an organic solvent at 25°C.
  • high solubility means the capability of the polymer to be dissolved in an organic solvent to form a homogenous solution (no suspension, no precipitate).
  • the polymeric dye according to the present invention can have a solubility ranging from at least about 1% (e.g., at least about 2%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight in an organic solvent at 25°C.
  • a solubility ranging from at least about 1% (e.g., at least about 2%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 90% (e.g.,
  • solubility refers to the weight percentage of a solute (e.g., a polymeric dye) based on the total weight of a solution (e.g., a solution containing the solute and an organic solvent) at 25°C.
  • a solute e.g., a polymeric dye
  • a solution e.g., a solution containing the solute and an organic solvent
  • the organic solvent in which the polymeric dye can be dissolved can include a ketone, an ester, an acetal, an ether, a carbonate, an ester, or a combination thereof.
  • suitable organic solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, cyclopentanone, acetone, methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol, dimethyl carbonate, propylene carbonate, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.
  • the organic solvent can include a single solvent or a combination of two or more (e.g., three or four) solvents.
  • the polymeric dye is substantially insoluble (e.g., having a solubility less than 0.1 wt%, preferably less than 0.01 wt%) in water at 25°C.
  • the polymeric dye of the present invention comprises :
  • the polymeric dye according to the present invention can be prepared with a method comprising the steps of:
  • the polymerizable monomer dye can be prepared by synthetic methods described herein or those known in the art.
  • the polymerizable monomer dye can be easily prepared by reaction of one reactive function, such as a hydroxyl group, an amine group, or a carboxyl group, of a dye with a reactive function of a polymerizable monomer, such as a carboxylic group, an acyl chloride, an anhydride group, an ester group, or a hydroxyl group, or an amine group.
  • one reactive function such as a hydroxyl group, an amine group, or a carboxyl group
  • a dye with a reactive function of a polymerizable monomer, such as a carboxylic group, an acyl chloride, an anhydride group, an ester group, or a hydroxyl group, or an amine group.
  • any dye as described above can be used provided that it contains at least one reactive function able to form a covalent bond with a reactive function of a polymerizable monomer.
  • the alkaline or alkaline-earth ion is preliminary replaced with a tetra alkyl ammonium group, such as for example, a tetra butyl ammonium group, a tetra hexyl ammonium group, or a tetra octyl ammonium group, for improving the solubility in organic solvent while decreasing the solubility in water.
  • the polymerizable monomer dye is obtained by reacting a dye having a hydroxyl group or a carboxylic group with a polymerizable monomer having a carboxylic group, an acyl chloride group, an anhydride group, an ester group, or an alcoholic or phenolic group.
  • the polymerizable monomer has a polymerizable function represented by a vinyl group.
  • the polymerizable monomer is an acrylic or methacrylic acid, or a derivative thereof, such as acrylate or methacrylate esters.
  • the reaction is conducted in a suitable solvent, preferably an aprotic solvent such as for example dichloromethane (DCM), acetone, acetonitrile, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.
  • a suitable solvent preferably an aprotic solvent such as for example dichloromethane (DCM), acetone, acetonitrile, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.
  • the reaction of the dye with the polymerizable monomer is an esterification reaction.
  • the esterification reaction is conducted in the presence of a carbodiimmide, such as for example, dicyclohexylcarbodiimide, N,N' diisopropylcarbodiimide (DIC), or 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide (EDC) as a coupling reagent, and 4-dimethylaminopyridine as a catalyst.
  • a carbodiimmide such as for example, dicyclohexylcarbodiimide, N,N' diisopropylcarbodiimide (DIC), or 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide (EDC) as a coupling reagent
  • DIC N,N' diisopropylcarbodiimide
  • EDC 1-ethyl-3-(3'-di
  • the resultant polymerizable monomer dye can be isolated from the reaction mixture by methods known in the art.
  • the resultant polymerizable monomer dye can be isolated by washing the reaction mixture with water and/or a brine solution, separating the organic layer from the aqueous layer, and removing the solvent from the organic layer (e.g., by evaporation).
  • the polymeric dye can be prepared by synthetic methods described herein or those known in the art.
  • copolymerization of one or more different polymerizable monomer dyes with polymerizable monomers can be realized by free-radical polymerization in a suitable solvent and in the presence of a suitable initiator.
  • the reaction is conducted in a suitable solvent, preferably an aprotic solvent such as for example dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.
  • a suitable solvent preferably an aprotic solvent such as for example dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.
  • the reaction may be started by thermal decomposition of an initiator (e.g., an organic peroxide (e.g., dicumyl peroxide) or an azo compound), photolysis (e.g., with metal iodides, metal alkyls or azo compounds (e.g., azoisobutylnitrile (AIBN))), a peroxide initiator (e.g., benzoyl peroxide), an initiator composition enabling a redox reaction (e.g., reduction of hydrogen peroxide or an alkyl hydrogen peroxide by means of iron ions or other reductants such as, e.g., Cr 2+ , V 2+ , Ti 3+ , Co 2+ or Cu + ), persulfate activation, ionizing radiation (e.g., by means of ⁇ -, ⁇ -, ⁇ - or x-rays), electrochemical activation, plasma activation, or sonication (e.g., at
  • the resultant polymeric dye can be isolated from the reaction mixture by methods known in the art.
  • the resultant polymeric dye can be isolated by precipitation in a solvent in which the polymeric dye is insoluble, and separating the precipitated polymer from the solvent by filtration, decantation or centrifugation.
  • reaction temperature for steps (1) and (2) can be adjusted as necessary. In some embodiments, both steps (1) and (2) can be performed at room temperature.
  • reaction time for steps (1) and (2) can be adjusted as necessary.
  • the progress of steps (1) can (2) can be monitored by UV-Vis spectroscopy, NMR spectroscopy, or thin layer chromatography (TLC) by using methods known in the art.
  • the polymeric dye according to the present invention can be formulated into an ink composition (e.g., an inkjet ink composition).
  • the ink composition can be a uniform solution, in which all solutes (including the polymeric dye according to the present invention) are dissolved.
  • the ink composition can be a dispersion or an emulsion.
  • the ink composition can be a solid composition.
  • the polymeric dye according to the present invention can range from at least about 1% (e.g., at least about 2%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 70% (e.g., at most about 65%, at most about 60%, at most about 55%, at most about 50%, at most about 45%, at most about 40%, at most about 35%, or at most about 30%) by weight of the ink composition.
  • at most about 70% e.g., at most about 65%, at most about 60%, at most about 55%, at most about 50%, at most about 45%, at most about 40%, at most about 35%, or at most about 30%
  • the polymeric dye according to the present invention can form an ink composition without using any metal (e.g., any heavy metal) or any colorant. Further, without wishing to be bound by theory, it is believed that an ink composition containing the polymeric dye according to the present invention can have excellent light fastness, color strength, and adhesion properties.
  • the ink composition described herein can include an organic solvent in which the polymeric dye according to the present invention is dissolved.
  • the organic solvent that is suitable for the ink composition can include a ketone, an ester, an acetal, an ether, a carbonate, an ester, or a combination thereof.
  • organic solvent examples include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, cyclopentanone, acetone, methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol, dimethyl carbonate, propylene carbonate, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.
  • the organic solvent can include one solvent or a combination of two or more (e.g., three or four) solvents.
  • the organic solvent can range from at least about 30% (e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%) by weight to at most about 99% (e.g., at most about 97%, at most about 95%, at most about 90%, at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, or at most about 60%) by weight of the ink composition.
  • at least about 30% e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%
  • at most about 99% e.g., at most about 97%, at most about 95%, at most about 90%, at most about 85%, at most about
  • the ink composition described herein can include a fusible carrier in which the polymeric dye according to the present invention is dispersed.
  • the fusible carrier that is suitable for the ink composition can include a wax, a resin and/or a long chain fatty acid, ester or alcohol.
  • suitable resins include without limitation copolyester resins, polyamide resins, rosin resins, polyesteramide resins, epoxy resins, polyvinylalcohol resins, cellulose esters, cellulose ethers and polyvinyl pyridine resins. These resins may be used alone or in combination.
  • suitable waxes include without limitation polyalkylene waxes, such as polyethylene waxes or polypropylene waxes, Fischer-Tropsch waxes, lineary primary alcohols, such as Unilin TM alcohol waxes (available from Baker Hughes), microcrystalline waxes, fatty acids, carnauba wax, candelilla wax, stearamides, paraffin wax and montan wax and ethoxylated long chain alcohols, such as Unithox TM (available from Baker Hughes).
  • the waxes may be used alone or in combination.
  • suitable long chain fatty acids, esters or alcohols include without limitation dialkyl ester of sebacic acid, higher aliphatic alcohol, stearic acid, lauric acid, and behenic acid.
  • a combination of waxes, resins and/or long chain fatty acids, esters or alcohols may be used.
  • the fusible carrier can range from at least about 30% (e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%) by weight to at most about 99% (e.g., at most about 97%, at most about 95%, at most about 90%, at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, or at most about 60%) by weight of the ink composition.
  • at least about 30% e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%
  • at most about 99% e.g., at most about 97%, at most about 95%, at most about 90%, at most about 85%, at
  • the ink composition described herein can include only two components (i.e., the polymeric dye according to the present invention and an organic solvent or a fusible carrier). In some embodiments, the ink composition can optionally include one or more (e.g., two, three, or four) additives or additional components.
  • the ink composition described herein can optionally include at least one conductivity salt.
  • suitable conductivity salts include alkali metal salts, alkaline earth salts and single or quaternary ammonium salts in the form of halides (chlorides, bromides, iodides and fluorides), perchlorates, nitrates, thiocyanates, formiates, acetates, sulphates, propionates, and the like.
  • the ink composition described herein can optionally include at least one rheology agent.
  • suitable rheology agents include nitrocellulose, cellulose acetate butyrate, cellulose acetate, shellac, a rosin ester, a polyurethane, an acrylic, or a conductive polymer (e.g., polyaniline).
  • the rheology agent can range from at least about 1% (e.g., at least about 2%, at least about 4%, at least about 5%, at least about 6%, at least about 8%, at least about 10%, or at least about 15%) by weight to at most about 30% (e.g., at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%) by weight of the ink composition.
  • at most about 30% e.g., at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%
  • adding a rheology agent in the ink composition described herein can increase the viscosity of the ink composition, provide structure for flow and drop formation, promote adhesion, slow or prevent separation of other ink components, and/or modify charge of the ink composition.
  • the ink composition described herein can optionally include at least one additional colorant, such as a dye or a pigment.
  • the dye or pigment can be either an organic or inorganic material.
  • the ink composition can be substantially free of a colorant other than the polymeric dye according to the present invention.
  • the ink composition described herein can optionally include one or more tackifiers.
  • a tackifier can improve adhesion between the ink composition and a substrate (e.g., a cardboard, a glass, a metal, or a film).
  • tackifiers include glycerol esters, pentaerythritol esters, hydrocarbons, rosin, rosin esters, modified rosin esters (e.g., hydrogenated, acid, or phenolic-modified rosin esters), cumarone-indene polymers, cyclic ketone polymers, styrene allyl alcohol polymers, polystyrenes, polyvinyl toluene/methylstyrene polymers, polyvinyl chloride, polyvinyl alcohol, ethylene/vinyl acetate, ethylene/acrylic acid, alkyl hydrocarbon polymers, aryl hydrocarbon polymers, alkyl aryl hydrocarbon polymers, terpene polymers, ethylene carbon monoxide copolymers, vinyl chloride/vinyl alcohol copolymers, polyvinyl butyral, polyketones, styrene/acrylic copolymers, polybutenes, polybutadie
  • the ink composition contains at least about 1 wt% (e.g., at least about 5 wt%, at least about 10 wt%, or at least about 15 wt%) and/or at most about 25 wt% (e.g., at most about 20 wt%, at most about 15 wt%, at most about 10 wt%, or at most about 5 wt%) of the tackifier.
  • the ink composition described herein can optionally include one or more resins (e.g., binder resins).
  • the resin can provide the ink composition with a desired viscosity, thermal stability, flexibility, and adhesion properties.
  • suitable resins include acacia (gum arabic); gum ghatti; guar gum; locust (carob) bean gum; karaya gum (sterculia gum); gum tragacanth; chicle; highly stabilized rosin ester; tall oil; manila copals; corn gluten; coumarone-indene resins; crown gum; damar gum; p, alpha-dimethylstyrene; gum elemi; ethylene oxide polymer and its adducts; ethylene oxide/propylene oxide copolymer and its adducts; galbanum resin; gellan gum; ghatti gum; gluten gum; guaiac gum; guarana gum; heptyl paraben
  • the ink composition includes enough resin to achieve the desired viscosity, stability, flexibility, and adhesion.
  • the ink composition contains at least about 1 wt% (e.g., at least about 5 wt%, at least about 10 wt%, or at least about 15 wt%) and/or at most about 25 wt% (e.g., at most about 20 wt%, at most about 15 wt%, at most about 10 wt%, or at most about 5 wt%) of the resin.
  • the ink composition is substantially free of any resin other than the polymeric dye according to the present invention.
  • the ink composition described herein can optionally include one or more plasticizers.
  • a plasticizer can reduce the viscosity of the ink composition.
  • plasticizers include aromatic sulfonamides, phthalates, acetates, adipates, amides, azelates, epoxides, glutarates, laurates, oleates, sebacates, stearates, sulfonates, tallates, phosphates, benzoin ethers, and trimellitates.
  • the ink composition contains at least about 1 wt% (e.g., at least about 2 wt%, at least about 4 wt%, at least about 6 wt%, or at least about 8 wt%) and/or at most about 10 wt% (e.g., at most about 9 wt%, at most about 7 wt%, at most about 5 wt%, or at most about 3 wt%) of the plasticizer.
  • the ink composition described herein can optionally include one or more antioxidants.
  • an antioxidant can inhibit oxidation (e.g., thermally induced oxidation) of the ink composition (e.g., when the ink composition is in a hot molten state during jetting).
  • antioxidants include butylated hydroxyanisole (BHA); butylated hydoxytoluene (BHT); propyl gallate; tert-butyl hydroquinone (TBHQ); ethyl enedi ami netetraacetic acid (EDTA); methyl paraben; and propyl paraben.
  • the ink composition contains at least about 0.1 wt% (e.g., at least about 0.5 wt%, at least about 1 wt%, or at least about 3 wt%) and at most about 5 wt% (e.g., at most about 4 wt%, at most about 3 wt%, at most about 2 wt%, or at most about 1 wt%) of the antioxidant.
  • the ink composition described herein can optionally include one or more dispersants.
  • a dispersant can assist in stabilizing an insoluble component (e.g., a colorant) in the ink composition.
  • the dispersant can prevent agglomeration of a colorant (e.g., a pigment) in the ink composition.
  • examples of dispersants include Solsperse 13,650, 13,940, 17,000, J910; Byk 108; Tego Dispers 700; UNIQEMA 5543; and EFKA 5244, 5207, 6750; which are all commercially available from Lubrizol; Byk; Evonik; Croda; and BASF, respectively.
  • the ink composition contains at least about 1 wt% (e.g., at least about 2 wt%, at least about 4 wt%, at least about 6 wt%, or at least about 8 wt%) and at most about 10 wt% (e.g., at most about 9 wt%, at most about 7 wt%, at most about 5 wt%, or at most about 3 wt%) of the dispersant.
  • the ink composition described herein can have any suitable apparent viscosity.
  • the ink composition can have an apparent viscosity ranging from at least about 1 centiPoise (cP) (e.g., at least about 5 cP, at least about 10 cP, at least about 15 cP, or at least about 20 cP) to at most about 25 cP (e.g., at most about 20 cP, at most about 15 cP, or at most about 10 cP) measured at 20°C and at 73 s -1 .
  • cP centiPoise
  • the ink composition described herein can optionally include one or more conductive agents.
  • the conductive agent can be a salt (e.g., an organic salt or an inorganic salt).
  • the salt can be a quaternary phosphonium salt (e.g., a tetraalkylphosphonium or tetraarylphosphonium salt), a quaternary ammonium salt (e.g., a tetraalkylammonium or tetraarylammonium salt), an imidazolium salt, or an alkali salt (e.g., a Li, Na, K, or Cs salt).
  • the ink composition described herein can have any suitable conductivity.
  • the ink composition can have a conductivity ranging from at least about 0 ⁇ S/cm (e.g., at least about 10 ⁇ S/cm, at least about 50 ⁇ S/cm, at least about 100 ⁇ S/cm, at least about 200 ⁇ S/cm, at least about 300 ⁇ S/cm, at least about 400 ⁇ S/cm at least about 500 ⁇ S/cm, or at least about 1000 ⁇ S/cm) to at most about 8000 ⁇ S/cm (e.g., at most about 7000 ⁇ S/cm, at most about 6000 ⁇ S/cm, at most about 5000 ⁇ S/cm, at most about 4000 ⁇ S/cm, at most about 3000 ⁇ S/cm, at most about 2000 ⁇ S/cm, or at most about 1000 ⁇ S/cm).
  • at least about 0 ⁇ S/cm e.g.,
  • the ink composition when the ink composition is designed for use in a continuous inkjet printing process, the ink composition can have a suitable conductivity (e.g., 100-8000 ⁇ S/cm) to enable the ink composition to be printed in this process.
  • a suitable conductivity e.g. 100-8000 ⁇ S/cm
  • the ink composition when the ink composition is designed for use in a thermal inkjet printing process, the ink composition can have zero conductivity since conductivity is not required in this printing process.
  • the ink composition is substantially free of a certain material.
  • the ink composition can be substantially free of a wax (e.g., a polyethylene wax), a colorant (e.g., a non-polymeric colorant) other than the polymeric dye according to the present invention, a resin (e.g., a non-polymeric resin) other than the polymeric dye according to the present invention, or a conductive agent (e.g., a salt).
  • a wax e.g., a polyethylene wax
  • a colorant e.g., a non-polymeric colorant
  • a resin e.g., a non-polymeric resin
  • a conductive agent e.g., a salt
  • the ink composition can be a solution (in which all solutes (e.g., a polymeric dye according to the present invention are dissolved) or a dispersion (which contains dispersed particles).
  • the ink composition described herein can be used in any suitable printing process, including a continuous inkjet (CIJ) printing process, a drop-on-demand printing process (e.g., thermal inkjet (TIJ) printing process or a piezo printing process), a hot-melt printing process, a valvejet printing process, a flexographic printing process, a lithographic printing process, a gravure printing process, a screen printing process, or a pad printing process, or an offset printing process.
  • the ink composition can be used in a printing process that includes ejecting the ink composition (either continuously or on demand) from a printhead in an inkjet printer onto a substrate to form an image.
  • a continuous stream of conductive ink droplets can be ejected from one or more nozzles of a printhead of an inkjet printer.
  • the droplets are electrostatically deflected to address several vertical pixels as the substrate moves relative to the nozzles.
  • CIJ inks generally have a suitable conductivity and allows the droplets to be deflected.
  • the process of jetting ink droplets continuously and directing unneeded drops to the gutter allows the CIJ systems to utilize fast evaporating solvents (e.g., those having a relative evaporation rate (RER) greater than 1 as determined by the ASTM method D3359 and relative to n-butyl acetate) without concern for decap (i.e., the ability to remain in the fluid condition in a printhead nozzle opening on exposure to air) and nozzle clogging, as the nozzles are effectively never idle during operation.
  • fast evaporating solvents e.g., those having a relative evaporation rate (RER) greater than 1 as determined by the ASTM method D3359 and relative to n-butyl acetate
  • decap i.e., the ability to remain in the fluid condition in a printhead nozzle opening on exposure to air
  • nozzle clogging as the nozzles are effectively never idle during operation.
  • a continuous ink stream ejected from a printhead is deviated by at least one electrode to which a static or sinusoidal high voltage is applied. Most of the ink stream is not printed and is directed to an ink recovery gutter.
  • segments of the ink stream are sampled asynchronously, deviated differently depending on their length (the length providing a means of varying the distribution of embedded electrical charge per unit length) and directed towards the substrate. These segments, which can be transformed into spherical drops under the effect of the surface tension, are separated from the jet before they are deflected such that their trajectory is different from the ink stream.
  • inks in a drop-on-demand printing process, inks can be jetted by either thermal inkjet cartridges or piezo drop-on-demand printheads.
  • an ink is loaded into a reservoir where it is either pumped or fed by gravity to a jetting chamber of a cartridge or printhead.
  • a liquid ink is ejected from a printhead by being rapidly heated, causing a rapid phase change from liquid to gas, thus causing a rapid volume expansion and subsequently causing a droplet to eject from an orifice.
  • a liquid ink is ejected from a printhead by activation of a piezo transformer (PZT), which causes a pressure wave to be exerted upon the ink and an ink droplet can be ejected from an orifice.
  • PZT piezo transformer
  • Both devices are referred to as drop-on-demand since a droplet of ink is ejected only when a heater or PZT material is activated.
  • Each cartridge or printhead contains an array of several orifices across its width. Activation of each orifice in such an array is performed methodically by the printer such that an image is formed drop-wise on a substrate, which is positioned a short distance from the orifice array.
  • the printers are designed such that an orifice array and a substrate move relative to one another in order to form an image.
  • This disclosure also features a product that includes a substrate and a solid ink defining an image on the substrate, in which the solid ink includes the ink composition described herein.
  • the substrate can be any suitable materials (e.g., porous or non-porous materials), such as films, coated and non-coated papers, plastics, glass, metals, and cardboards.
  • the substrate can be a package material, such as a cardboard (e.g., a corrugated cardboard) or a film (e.g., a shrink wrap).
  • suitable substrates include flexible packaging films (e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, or poly(lactic acid) films), rigid plastic materials (e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, poly(lactic acid), polyvinylchloride materials), corrugated cardboard (e.g., bleached, unbleached, and coated cardboard), boxboard (e.g., glossy coated, matte coated, and uncoated boxboards), bottle materials (e.g., glass, polyethylene terephthalate, polyethylene, polypropylene, and poly(lactic acid) materials).
  • flexible packaging films e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, or poly(lactic acid) films
  • rigid plastic materials e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, poly(lactic acid), polyvinylch
  • the title product is obtained by reacting the Disperse Red 1 with methacryloyloxyethylsuccinic acid according to the following reaction.
  • the title product is obtained by reacting the Blue Patent V with methacryloyloxyethylsuccinic acid according to the following reaction.
  • the first step consists in the substitution of the sodium counter-ion with tetrabutyl ammonium to decrease the hydrophilic character of Patent Blue V.
  • Patent blue V sodium salt (20.0 g, 0.034 mol, 1 eq)
  • Tetra-n-butylammonium bromide (22.1 g, 0.069 mol, 2 eq)
  • the biphasic mixture was vigorously stirred for 3 hours at room temperature, then 1L of dichloromethane and 400 mL of HCl 0.5M were added before transferring the solution in a separatory funnel.
  • the second step consists in the reaction between the dye and the polymerizable monomer.
  • the product of the step one (20.9 g, 16.9 mmol, 1 eq) and 2-(methacryloyloxy)ethyl succinate (4.28 g, 18.6 mmol, 1.1 eq) were dissolved in 150 mL of dichloromethane.
  • the mixture was cooled down to 0°C with an ice bath, then EDC.HCl (3.9 g, 20.4 mmol,1.2 eq) and DMAP (0.41 g, 3.4 mmol, 0.2 eq) were successively added in small portions under nitrogen flow.
  • the title product is obtained by reacting the solvent violet 13 with methacryloyloxyethylsuccinic acid according to the following reaction.
  • the title product is obtained by reacting the disperse red 60 with methacryloyloxyethylsuccinic acid according to the following reaction.
  • Disperse Red 60 (10.0 g, 28.4 mmol) and 2-(Methacryloyloxy)ethyl succinate (7.84 g, 34.1 mmol) were dissolved in 40 mL of dichloromethane. The mixture was cooled down to 0°C and deoxygenated under nitrogen flow, then, EDC.HCl (7.60 g, 39.6 mmol) and DMAP (1.74 g, 14.2 mmol) were added. The mixture was then heated to 40°C and left under magnetic stirring for 8h.
  • the product was dissolved in dichloromethane and precipitated twice in a cold mixture of MeOH/Et 2 O 3/7 v/v then once in pentane. After drying in an oven at 40°C, the polymer was obtained as a black powder.
  • the polymeric dye showed a IWS value of 2, evaluated as described in the ISO 12040 standard.
  • a red polymeric dye was obtained by free-radical polymerization according to the following scheme.
  • the polymer was let to settle, and the supernatant solvent was removed. After drying in an oven at 40°C, the polymer was obtained as a dark red powder.
  • the polymeric dye showed a IWS value of 3, evaluated as described in the ISO 12040 standard.
  • Patent Blue V Methacryloyloxyethylsuccinate (3.0 g, 1.48 mmol), Solvent Violet 13 Methacryloyloxyethylsuccinate (1.4 g, 2.11 mmol), ethyl methacrylate (3.0 g, 26.4 mmol) and AIBN (98 mg, 0.60 mmol) were dissolved in 32 mL of DMF.
  • the mixture was deoxygenated under argon flux for 30 min at room temperature, then the polymerization was performed at 80°C overnight. When the polymerization was complete, DMF was removed by evaporation under vacuum.
  • a red polymeric dye was obtained by free-radical polymerization according to the following scheme.
  • Patent Blue V Methacryloyloxyethylsuccinate 1.0 g, 0.495 mmol
  • Disperse Red 60 Methacryloyloxyethylsuccinate 2.3 g, 3.8 mmol
  • ethyl methacrylate 2.7 g, 23.8 mmol
  • AIBN 92 mg, 0.56 mmol
  • the product was dissolved in dichloromethane and precipitated twice in a mixture of Methanol / Diethyl ether 2:8 v/v then once in diethyl ether. After drying in an oven at 50°C, the polymer was obtained as a dark green powder.
  • An inkjet ink has been prepared by dissolving different amount of the black polymeric dye of example 5 in methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • a coating was done on white sealed cardboard (opacity cards of Leneta supplier) using a wet film deposit of 12 ⁇ m and a standard coating speed of 15m/min.
  • the following table 1 summarizes the lightness (L*) evaluated on coating and the viscosity (cP) of the resulting ink at the several weight percentages.
  • L* lightness
  • cP viscosity
  • An inkjet ink has been prepared by dissolving a conductive agent (1%wt) and the black polymeric dye of example 5 (12,5%wt) in MEK.
  • the light fastness resistance was visually evaluated by comparing pictures taken at different times of storage in a sun test apparatus at an irradiance of 60 ⁇ 2 W/m 2 and a temperature of 65 ⁇ 3°C as described in the ISO 16474-2 standard. The results are illustrated in Figures 2-6 .
  • results illustrated in figures 2-6 correspond to a decrease of 30% of the color strength of the printed sample after at least two years.
  • An inkjet ink according to the present invention (INK1) has been prepared by dissolving the black polymeric dye of example 5 at 15% by weight in methyl ethyl ketone (MEK).
  • Two reference inkjet inks have been prepared by dissolving the commercial Solvent Black27 (INK2) and Solvent Black 27 (INK3) dyes at 6% by weight and a polymeric resin at 9% by weight in MEK.
  • the polymeric resin is a solution of nitrocellulose in isopropyl alcohol with a ratio nitrocellulose to isopropyl alcohol equal to 70:30.
  • Shear viscosity was measured by using a shear rate of 73 s-1 at 20°C as described in standard DIN 53019-1 (e.g., by using a viscometer with coaxial cylinders of the "Couette" type).
  • L* Lightness measurements were done with a CIELAB (or CIE L*a*b*) spectrophotometer (e.g., an X- Rite eXact instrument).
  • CIELAB space is defined in three dimensions where L* is related to the lightness, a* is the red/green color parameter and b* is the yellow/blue color parameter.
  • a black polymeric dye was obtained by free-radical polymerization according to the following scheme.
  • Patent Blue V Methacryloyloxyethylsuccinate, ethyl methacrylate, Disperse Red 1 Methacryloyloxyethylsuccinate, dodecanthiol and AIBN (2 mol% to monomers) were dissolved in DMF (dry extract 20 wt%).
  • the mixture was deoxygenated under argon flow for 15 min at room temperature, then the polymerization was performed at 70°C. After reaching a conversion of about 80%, portions of AIBN were added to increase the conversion higher than 95 %.
  • a black polymeric dye was obtained by free-radical polymerization according to the following scheme.
  • Patent Blue V Methacryloyloxyethylsuccinate 2.0 g, 1.27 mmol
  • Disperse Red 1 Methacryloyloxyethylsuccinate (1.37 g, 2.54 mmol
  • butyl methacrylate (5.49 g, 38.6 mmol)
  • AIBN 70.0 mg, 0.42 mmol
  • the mixture was deoxygenated under argon flux for 15 min at room temperature, then the polymerization was performed at 70°C overnight.
  • DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane then precipitated in pentane.
  • the polymer was then let to settle, and the supernatant solvent was removed. After drying in an oven at 40°C, the polymer was obtained as a black powder.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates to a polymeric dye as well as to related ink compositions, products, and processes.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a polymeric dye as well as to related ink compositions, products, and processes.
  • More in particular, the present invention relates to a polymeric dye resulting from the polymerization of polymerizable monomers bearing a polymerizable function, such as acrylate, methacrylate, acrylamide, or methacrylamide, and a chromophore function.
    • STATE OF THE ART
  • During inkjet printing, the ink is typically ejected through a component of a printhead (e.g., an array of nozzles) onto a substrate. Many solvent-soluble dyes currently used in the inkjet printing have been identified as materials hazardous for human and environment with long-term compliance issues.
  • These dyes are typically coordinated to heavy metals, which could contribute to the toxicity of such dyes.
  • Current black dyes used for inkjet printing are organometallic complexes. Organic part contains diazo function, and the metallic cation is trivalent chromium ion.
  • Several colored dyes, such as blue and red dyes, also include metallic cations, like copper, cobalt and iron.
  • This type of chemistry raised some concerns for human health and some dyes are already classified CMR (Carcinogenic, Mutagenic, Reprotoxic).
  • As chemicals could migrate through the packaging substrate and therefore be found in the product, CMR chemicals (as dyes) are banned from sensitive markets such as from food, pharmaceutical, and cosmetic industries.
  • As described by the REACh regulations, it would be desirable to have a polymeric dye because high molecular weight molecules such as polymers do not migrate through packaging substrates and would be considered safe for sensitive markets such as from food, pharmaceutical, and cosmetic industries.
  • Colored polymeric dyes are known in the art such as for example, from US7732509B2 , US7273897B2 , WO03089533 , WO9961533 , DE19651689 , CN108071023B and CN101787222A . However, such documents mainly disclose water-soluble polymeric dyes.
  • Thus, there is a need to develop organic solvent-soluble polymeric dyes that do not contain heavy metals.
    • SUMMARY OF THE INVENTION
  • The Applicant has faced the problem of developing organic solvent-soluble polymeric dyes that do not contain heavy metals.
  • After extensive experimentation, the Applicant has found a solution allowing to get an organic solvent-soluble polymeric dye that does not contain heavy metals.
  • The solution comprises a method for synthetizing a polymeric dye comprising the steps of:
    1. (1) functionalizing a dye with a polymerizable function to get a polymerizable monomer dye, and
    2. (2) copolymerizing at least one polymerizable monomer dye with polymerizable monomers, and
    3. (3) recovering the resulting polymeric dye.
  • The polymerizable monomer dye can be easily prepared by reaction of one reactive function, such as a hydroxyl group, an amine group, or a carboxyl group, of a dye with a reactive function of a polymerizable monomer, such as an acyl chloride or an anhydride or an ester or a carboxylic acid, or a hydroxyl group, or an amine group.
  • The copolymerization of at least one polymerizable monomer dye with polymerizable monomers can be easily conducted in the presence of a suitable initiator in a suitable solvent.
  • The Applicant has found that by copolymerizing two or more polymerizable monomer dyes having different chromophores, a wide range of polymeric dyes having different colors (black, cyan, magenta, yellow, blue, red, and green) can be obtained.
  • In one aspect, the present invention relates to a polymeric dye and to the preparation process thereof.
  • Such a polymeric dye can be used as a dye in a continuous inkjet (CIJ) printing process or a drop-on-demand (DOD) printing process (e.g., a thermal inkjet (TIJ) printing process) or a hot melt (HM) inkjet printing process. Compared to conventional colorants (e.g., carbon black and metal complexed dyes) used in printing processes (e.g., CIJ, DOD, TIJ, or HM), the polymeric dye of the present invention can form an ink composition without including any toxic metallic cation and with fair fastness, while still possessing excellent stability, printability, solubility in organic solvent, and adhesion to a variety of substrates.
  • In another aspect, the present invention relates to an ink composition that includes the polymeric dye of the present invention, and an organic solvent. The composition can be a solution.
  • The polymeric dye of the present invention can be in an amount of from about 1 % to about 70% by weight, preferably from 3% to 50% by weight, with respect to the weight of the ink composition.
  • In another aspect, the present invention relates to a product that includes a substrate (e.g., a cardboard, a glass, a metal, or a film) and a solid ink defining an image on the substrate, in which the solid ink includes the ink composition described herein.
  • In another aspect, the present invention relates to a printing process that includes ejecting the ink composition described herein from a printhead in an inkjet printer onto a substrate to form an image.
    • BRIEF DESCRIPTION OF THE FIGURES
  • Figures 1 to 6 shows the results of the printing test as described in example 10 immediately after printing (Figure 1) and after 10, 18, 28, 35, and 50 hours of lightfastness aging (Figures 2-6, respectively).
    • DETAILED DESCRIPTION OF THE INVENTION
  • While this invention can be implemented in many different forms, specific embodiments thereof are shown in the drawings and will be further described herein with the understanding that the present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.
    • Polymeric Dye
  • In an embodiment, the polymeric dye according to the present invention is a co-polymer comprising the monomer repeating units having the following formulas (I) and (II):
    Figure imgb0001
     wherein M1 and M2, equal or different each other, are reactive monomers, and C1 and C2, different each other, are chromophore units.
  • According to an embodiment, the polymeric dye according to the present invention can optionally comprises the monomer repeating units having the following formulas (III) and (IV):
    Figure imgb0002
     wherein M3 and M4, equal or different each other, are reactive monomers, and C3 is a chromophore unit different from C1 and C2.
  • In an embodiment of the present invention, the polymeric dye can optionally comprise the monomer repeating unit having the following formulas (V):
    Figure imgb0003
     wherein M5 is a reactive monomer, and C4 is a chromophore unit different from C1-C3.
  • In an embodiment of the present invention, M1 to M5, equal or different each other, are selected from the group consisting of acrylic acid monomer, methacrylic acid monomer, acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, vinyl alcohol monomer, vinyl amine monomer, and the like.
  • In an embodiment of the present invention, any one of C1-C4 can be a blue chromophore unit derived from a commercial dye selected from the group consisting of:
    • Acid Blue 1, 3, 7, 9, 15, 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 52, 57, 58, 61:1, 62, 62:1, 63, 64, 65, 68, 69, 72, 74, 78, 78:1, 79, 80, 81, 81:1, 83, 90, 92, 96, 103, 104, 111, 112, 113, 114, 120, 124, 127, 127:1, 128, 129, 129:1, 138, 138:1, 140, 142, 145, 150, 156, 158, 171, 175, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 215, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 277, 277:1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 344, 350;
    • Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29;
    • Direct Blue 1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98,106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218, 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291;
    • Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 77, 79, 79:1, 79:2, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 281, 284, 285, 287, 288, 291, 291:1, 293, 295, 297, 301, 315, 330, 333, 373;
    • Food Blue 1, 2;
    • Reactive Blue 2, 3, 4, 5, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79, 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194, 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236;
    • Solvent Blue 4, 5, 6, 35, 38, 48, 59, 67, 70, 104, and 136.
  • In an embodiment of the present invention, any one of C1-C4 can be a red chromophore unit derived from a commercial dye selected from the group consisting of:
    • Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97:1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 143:1, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415, 447;
    • Basic Red 1, 2, 9, 12, 13, 37;
    • Direct Red 2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243, 254;
    • Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328, 337, 343;
    • Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105, 106;
    • Reactive Red 2, 3, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78, 83, 84, 106, 111, 312, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180,183, 184, 187, 190, 193, 194, 195, 198, 218, 220, 222, 223, 228, 235;
    • Solvent Red 1, 23, 29, 49, 119, 122, 125, 127, 130, 132, 135, 149, 160, 164, 168, 169, 172 and 233.
  • In an embodiment of the present invention, any one of C1-C4 can be a green chromophore unit derived from a commercial dye selected from the group consisting of:
    • Acid Green 1, 3, 5, 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 50, 56, 73, 81, 84, 104, 108, 109;
    • Basic Green 1, 4, 5;
    • Direct Green 26, 28, 59, 80, 85;
    • Disperse Green 9;
    • Food Green 2, 3;
    • Reactive Green 5, 7, 8, 12, 15, 19, 21;
    • Solvent Green 1, 3, 7, and 11.
  • In an embodiment of the present invention, any one of C1-C4 can be a chromophore unit derived from a commercial dye selected from the group consisting of:
    • Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40:1, 42, 44, 49, 59, 59:1, 61, 65, 72, 73, 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219:1, 220, 230, 232, 235, 241, 242, 246;
    • Basic Yellow 1, 2, 11, 12, 14, 21, 28, 32, 36, 57, 87;
    • Direct Yellow 4, 7, 8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 59, 62, 79, 86, 87, 98, 105, 106, 130, 132, 137, 142, 147, 153;
    • Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227, 231, 232;
    • Food Yellow 3, 4, 5;
    • Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102, 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176;
    • Solvent Yellow 2, 3, 7, 10, 13, 14, 19, 25, 28, 33, 88, 89, 114, 146, 163;
    • Acid Orange 3, 6, 7, 8, 10, 12, 19, 20, 24, 51, 56, 63, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, 144, 149, 152, 156, 162, 166, 168;
    • Basic Orange 2, 14, 15, 21, 22, 31, 69;
    • Direct Orange 6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118;
    • Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142;
    • Reactive Orange 1, 4, 5, 7, 11, 2, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92, 93, 95, 107;
    • Solvent Orange 1, 2, 3, 7, 11, 15, 20, 25, 54, 60, 62, 63, 86, 99, 105;
    • Acid Violet 7, 9, 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126;
    • Basic Violet 1, 2, 3, 4, 7, 10, 14;
    • Direct Violet 9, 35, 51, 66, 94, 95;
    • Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77;
    • Food Violet 2;
    • Reactive Violet 1, 2, 4, 5, 6, 8, 9, 22, 23, 33, 36, 38;
    • Solvent Violet 8, 9, 11, 13, 14, and 38.
  • Amongst the commercial dyes listed above, the preferred commercial dyes are those including at least one reactive function, such as a hydroxyl group, an amine group, or a carboxyl group, able to react with a reactive function of a polymerizable monomer. However, commercial dyes not having any reactive function can be used for the scope of the present invention by derivatization to include a reactive function.
  • In some embodiments, the polymeric dye according to the present invention can be a block copolymer, a random copolymer, or a graft copolymer. In a preferred embodiment, the polymeric dye according to the present invention is a random copolymer.
  • In some embodiments, the polymeric dye according to the present invention can have a weight average molecular weight of at least about 1,000 Da (e.g., at least about 2,000 Da, at least about 5,000 Da, at least about 7,500 Da, at least about 10,000 Da, at least about 12,500 Da, at least about 15,000 Da, at least about 17,500 Da, or at least about 20,000 Da) to at most about 120,000 Da (e.g., at most about 115,000 Da, at most about 110,000 Da, at most about 105,000 Da, at most about 100,000 Da, at most about 95,000 Da, or at most about 90,000 Da).
  • In some embodiments, the polymeric dye according to the present invention can comprise an amount of any one of the monomer repeating units having the formulas (I) to (V) of from at least about 5% (e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 80% (e.g., at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight with respect to the weight average molecular weight of the polymeric dye.
  • In an embodiment, the polymeric dye according to the present invention comprises an amount of any one of the monomer repeating units having the formulas (I), (II) and (IV) of from at least about 5% (e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 80% (e.g., at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight with respect to the weight average molecular weight of the polymeric dye.
  • In some embodiments, the polymeric dye according to the present invention comprises a total amount of monomer repeating units having the formulas (I) and (II) of from at least about 10% (e.g., at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight with respect to the weight average molecular weight polymeric dye, the remaining amount being represented by monomer repeating units having the formula (IV), and optionally by monomer repeating units having the formulas (III) and (V).
  • In general, the polymeric dye according to the present invention can have a relatively high solubility in an organic solvent at 25°C. The term "high solubility" means the capability of the polymer to be dissolved in an organic solvent to form a homogenous solution (no suspension, no precipitate).
  • In some embodiments, the polymeric dye according to the present invention can have a solubility ranging from at least about 1% (e.g., at least about 2%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, at most about 60%, at most about 55%, or at most about 50%) by weight in an organic solvent at 25°C. As used herein, the solubility mentioned herein refers to the weight percentage of a solute (e.g., a polymeric dye) based on the total weight of a solution (e.g., a solution containing the solute and an organic solvent) at 25°C.
  • In some embodiments, the organic solvent in which the polymeric dye can be dissolved can include a ketone, an ester, an acetal, an ether, a carbonate, an ester, or a combination thereof. Examples of suitable organic solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, cyclopentanone, acetone, methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol, dimethyl carbonate, propylene carbonate, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. In some embodiments, the organic solvent can include a single solvent or a combination of two or more (e.g., three or four) solvents.
  • In some embodiments, the polymeric dye is substantially insoluble (e.g., having a solubility less than 0.1 wt%, preferably less than 0.01 wt%) in water at 25°C.
  • In an embodiment, the polymeric dye of the present invention comprises :
    • at least one monomer repeating unit having the following formula (I) to (III) and (V):
      Figure imgb0004
       wherein M1, M2, M3, and M5, equal or different each other, are reactive monomers as described above, and C1 to C4, different each other, are chromophore units as described above, and
    • a monomer repeating unit having the following formula (IV):
      Figure imgb0005
      • wherein M4 is a reactive monomer as described above, and
      • wherein said polymeric dye is soluble in organic solvent, preferably having a solubility in an organic solvent at 25°C of at least 1 wt%, and insoluble in water, preferably having a solubility in water at 25°C of less than 0.1 wt%.
    Method of Making Polymeric dye
  • The polymeric dye according to the present invention can be prepared with a method comprising the steps of:
    1. (1) functionalizing a dye with a polymerizable function to get a polymerizable monomer dye,
    2. (2) copolymerizing at least one polymerizable monomer dye with polymerizable monomers, and
    3. (3) recovering the resulting polymeric dye.
  • The polymerizable monomer dye can be prepared by synthetic methods described herein or those known in the art.
  • The polymerizable monomer dye can be easily prepared by reaction of one reactive function, such as a hydroxyl group, an amine group, or a carboxyl group, of a dye with a reactive function of a polymerizable monomer, such as a carboxylic group, an acyl chloride, an anhydride group, an ester group, or a hydroxyl group, or an amine group.
  • Any dye as described above can be used provided that it contains at least one reactive function able to form a covalent bond with a reactive function of a polymerizable monomer. In some embodiments, when a dye comprises alkaline or alkaline-earth sulfonate or carboxylate groups, the alkaline or alkaline-earth ion is preliminary replaced with a tetra alkyl ammonium group, such as for example, a tetra butyl ammonium group, a tetra hexyl ammonium group, or a tetra octyl ammonium group, for improving the solubility in organic solvent while decreasing the solubility in water.
  • In some embodiments, the polymerizable monomer dye is obtained by reacting a dye having a hydroxyl group or a carboxylic group with a polymerizable monomer having a carboxylic group, an acyl chloride group, an anhydride group, an ester group, or an alcoholic or phenolic group.
  • In some embodiments, the polymerizable monomer has a polymerizable function represented by a vinyl group. In a preferred embodiment, the polymerizable monomer is an acrylic or methacrylic acid, or a derivative thereof, such as acrylate or methacrylate esters.
  • In some embodiments, the reaction is conducted in a suitable solvent, preferably an aprotic solvent such as for example dichloromethane (DCM), acetone, acetonitrile, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.
  • In some embodiments, the reaction of the dye with the polymerizable monomer is an esterification reaction. In a preferred embodiment, the esterification reaction is conducted in the presence of a carbodiimmide, such as for example, dicyclohexylcarbodiimide, N,N' diisopropylcarbodiimide (DIC), or 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide (EDC) as a coupling reagent, and 4-dimethylaminopyridine as a catalyst.
  • The resultant polymerizable monomer dye can be isolated from the reaction mixture by methods known in the art. For example, the resultant polymerizable monomer dye can be isolated by washing the reaction mixture with water and/or a brine solution, separating the organic layer from the aqueous layer, and removing the solvent from the organic layer (e.g., by evaporation).
  • Starting from one or more different polymerizable monomer dyes, the polymeric dye can be prepared by synthetic methods described herein or those known in the art.
  • The copolymerization of one or more different polymerizable monomer dyes with polymerizable monomers can be realized by free-radical polymerization in a suitable solvent and in the presence of a suitable initiator.
  • In some embodiments, the reaction is conducted in a suitable solvent, preferably an aprotic solvent such as for example dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.
  • In some embodiments, the reaction may be started by thermal decomposition of an initiator (e.g., an organic peroxide (e.g., dicumyl peroxide) or an azo compound), photolysis (e.g., with metal iodides, metal alkyls or azo compounds (e.g., azoisobutylnitrile (AIBN))), a peroxide initiator (e.g., benzoyl peroxide), an initiator composition enabling a redox reaction (e.g., reduction of hydrogen peroxide or an alkyl hydrogen peroxide by means of iron ions or other reductants such as, e.g., Cr2+, V2+, Ti3+, Co2+ or Cu+), persulfate activation, ionizing radiation (e.g., by means of α-, β-, γ- or x-rays), electrochemical activation, plasma activation, or sonication (e.g., at around 16 kHz).
  • The resultant polymeric dye can be isolated from the reaction mixture by methods known in the art. For example, the resultant polymeric dye can be isolated by precipitation in a solvent in which the polymeric dye is insoluble, and separating the precipitated polymer from the solvent by filtration, decantation or centrifugation.
  • In general, the reaction temperature for steps (1) and (2) can be adjusted as necessary. In some embodiments, both steps (1) and (2) can be performed at room temperature.
  • In general, the reaction time for steps (1) and (2) can be adjusted as necessary. The progress of steps (1) can (2) can be monitored by UV-Vis spectroscopy, NMR spectroscopy, or thin layer chromatography (TLC) by using methods known in the art.
    • Ink Composition
  • In general, the polymeric dye according to the present invention can be formulated into an ink composition (e.g., an inkjet ink composition). In some embodiments, the ink composition can be a uniform solution, in which all solutes (including the polymeric dye according to the present invention) are dissolved. In some embodiments, the ink composition can be a dispersion or an emulsion. In some further embodiments, the ink composition can be a solid composition.
  • In some embodiments, the polymeric dye according to the present invention can range from at least about 1% (e.g., at least about 2%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) by weight to at most about 70% (e.g., at most about 65%, at most about 60%, at most about 55%, at most about 50%, at most about 45%, at most about 40%, at most about 35%, or at most about 30%) by weight of the ink composition.
  • Without wishing to be bound by theory, it is believed that the polymeric dye according to the present invention can form an ink composition without using any metal (e.g., any heavy metal) or any colorant. Further, without wishing to be bound by theory, it is believed that an ink composition containing the polymeric dye according to the present invention can have excellent light fastness, color strength, and adhesion properties.
  • In some embodiments, the ink composition described herein can include an organic solvent in which the polymeric dye according to the present invention is dissolved. In some embodiments, the organic solvent that is suitable for the ink composition can include a ketone, an ester, an acetal, an ether, a carbonate, an ester, or a combination thereof. Examples of suitable organic solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, cyclopentanone, acetone, methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol, dimethyl carbonate, propylene carbonate, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. In some embodiments, the organic solvent can include one solvent or a combination of two or more (e.g., three or four) solvents.
  • In some embodiments, the organic solvent can range from at least about 30% (e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%) by weight to at most about 99% (e.g., at most about 97%, at most about 95%, at most about 90%, at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, or at most about 60%) by weight of the ink composition.
  • In some embodiments, the ink composition described herein can include a fusible carrier in which the polymeric dye according to the present invention is dispersed. In some embodiments, the fusible carrier that is suitable for the ink composition can include a wax, a resin and/or a long chain fatty acid, ester or alcohol. Examples of suitable resins include without limitation copolyester resins, polyamide resins, rosin resins, polyesteramide resins, epoxy resins, polyvinylalcohol resins, cellulose esters, cellulose ethers and polyvinyl pyridine resins. These resins may be used alone or in combination. Examples of suitable waxes include without limitation polyalkylene waxes, such as polyethylene waxes or polypropylene waxes, Fischer-Tropsch waxes, lineary primary alcohols, such as Unilin™ alcohol waxes (available from Baker Hughes), microcrystalline waxes, fatty acids, carnauba wax, candelilla wax, stearamides, paraffin wax and montan wax and ethoxylated long chain alcohols, such as Unithox™ (available from Baker Hughes). The waxes may be used alone or in combination. Examples of suitable long chain fatty acids, esters or alcohols include without limitation dialkyl ester of sebacic acid, higher aliphatic alcohol, stearic acid, lauric acid, and behenic acid. Moreover, a combination of waxes, resins and/or long chain fatty acids, esters or alcohols may be used.
  • In some embodiments, the fusible carrier can range from at least about 30% (e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%) by weight to at most about 99% (e.g., at most about 97%, at most about 95%, at most about 90%, at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, or at most about 60%) by weight of the ink composition.
  • In some embodiments, the ink composition described herein can include only two components (i.e., the polymeric dye according to the present invention and an organic solvent or a fusible carrier). In some embodiments, the ink composition can optionally include one or more (e.g., two, three, or four) additives or additional components.
  • In some embodiments, the ink composition described herein can optionally include at least one conductivity salt. Examples of suitable conductivity salts include alkali metal salts, alkaline earth salts and single or quaternary ammonium salts in the form of halides (chlorides, bromides, iodides and fluorides), perchlorates, nitrates, thiocyanates, formiates, acetates, sulphates, propionates, and the like.
  • In some embodiments, the ink composition described herein can optionally include at least one rheology agent. Examples of suitable rheology agents include nitrocellulose, cellulose acetate butyrate, cellulose acetate, shellac, a rosin ester, a polyurethane, an acrylic, or a conductive polymer (e.g., polyaniline). In some embodiments, the rheology agent can range from at least about 1% (e.g., at least about 2%, at least about 4%, at least about 5%, at least about 6%, at least about 8%, at least about 10%, or at least about 15%) by weight to at most about 30% (e.g., at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%) by weight of the ink composition. Without wishing to be bound by theory, it is believed that adding a rheology agent in the ink composition described herein can increase the viscosity of the ink composition, provide structure for flow and drop formation, promote adhesion, slow or prevent separation of other ink components, and/or modify charge of the ink composition.
  • In some embodiments, the ink composition described herein can optionally include at least one additional colorant, such as a dye or a pigment. The dye or pigment can be either an organic or inorganic material. In some embodiments, the ink composition can be substantially free of a colorant other than the polymeric dye according to the present invention.
  • In some embodiments, the ink composition described herein can optionally include one or more tackifiers. In general, a tackifier can improve adhesion between the ink composition and a substrate (e.g., a cardboard, a glass, a metal, or a film). Examples of tackifiers include glycerol esters, pentaerythritol esters, hydrocarbons, rosin, rosin esters, modified rosin esters (e.g., hydrogenated, acid, or phenolic-modified rosin esters), cumarone-indene polymers, cyclic ketone polymers, styrene allyl alcohol polymers, polystyrenes, polyvinyl toluene/methylstyrene polymers, polyvinyl chloride, polyvinyl alcohol, ethylene/vinyl acetate, ethylene/acrylic acid, alkyl hydrocarbon polymers, aryl hydrocarbon polymers, alkyl aryl hydrocarbon polymers, terpene polymers, ethylene carbon monoxide copolymers, vinyl chloride/vinyl alcohol copolymers, polyvinyl butyral, polyketones, styrene/acrylic copolymers, polybutenes, polybutadienes, styrene- isoprene-styrene, styrene-butadiene- styrene, polyvinyl pyrrolidone, polyvinyl pyridine, vinyl pyrrolidone/vinyl acetate, polyurethanes, polyesters, polyamides, cellulose esters, cellulose ethers, polyols, styrene-acrylates, polypropylene, chlorinated polypropylene, chlorinated paraffin, gilsonite and other asphaltic materials, cyclic hydrocarbon polymer, halogenated polymers, acrylics, epoxides, novolacs, and other synthetic and natural resins. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 5 wt%, at least about 10 wt%, or at least about 15 wt%) and/or at most about 25 wt% (e.g., at most about 20 wt%, at most about 15 wt%, at most about 10 wt%, or at most about 5 wt%) of the tackifier.
  • In some embodiments, the ink composition described herein can optionally include one or more resins (e.g., binder resins). The resin can provide the ink composition with a desired viscosity, thermal stability, flexibility, and adhesion properties. Examples of suitable resins include acacia (gum arabic); gum ghatti; guar gum; locust (carob) bean gum; karaya gum (sterculia gum); gum tragacanth; chicle; highly stabilized rosin ester; tall oil; manila copals; corn gluten; coumarone-indene resins; crown gum; damar gum; p, alpha-dimethylstyrene; gum elemi; ethylene oxide polymer and its adducts; ethylene oxide/propylene oxide copolymer and its adducts; galbanum resin; gellan gum; ghatti gum; gluten gum; guaiac gum; guarana gum; heptyl paraben; cellulose resins, including methyl and hydroxypropyl; hydroxypropyl methylcellulose resins; isobutyl ene-isoprene copolymer; mastic gum; oat gum; opopanax gum; polyacrylamide; modified polyacrylamide resin; polylimonene; polyisobutylene; polymaleic acid; polyoxyethylene derivatives; polypropylene glycol; polyvinyl acetate; polyvinyl alcohol; polyvinyl polypyrrolidone; polyvinyl pyrrolidone; rosin, adduct with fumaric acid, pentaerythritol ester; rosin, gum, glycerol ester; rosin, gum or wood, pentaerythritol ester; rosin, gum or wood, partially hydrogenated, glycerol ester; rosin, gum or wood, partially hydrogenated, pentaerythritol ester; rosin, methyl ester, partially hydrogenated; rosin, partially dimerized, glycerol ester; rosin, partially hydrogenated; rosin and rosin derivatives; rosin, polymerized, glycerol ester; rosin, tall oil, glycerol ester; rosin, wood; rosin, wood, glycerol ester; purified shellac; styrene; styrene terpolymers; styrene copolymers; sucrose acetate isobutyrate; terpene resins, natural and synthetic; turpentine gum; vinylacetate; vinyl chloride-vinylidene chloride copolymer; xanthan gum; and zein. In some embodiments, the ink composition includes enough resin to achieve the desired viscosity, stability, flexibility, and adhesion. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 5 wt%, at least about 10 wt%, or at least about 15 wt%) and/or at most about 25 wt% (e.g., at most about 20 wt%, at most about 15 wt%, at most about 10 wt%, or at most about 5 wt%) of the resin. In some embodiments, the ink composition is substantially free of any resin other than the polymeric dye according to the present invention.
  • In some embodiments, the ink composition described herein can optionally include one or more plasticizers. In general, a plasticizer can reduce the viscosity of the ink composition. Examples of plasticizers include aromatic sulfonamides, phthalates, acetates, adipates, amides, azelates, epoxides, glutarates, laurates, oleates, sebacates, stearates, sulfonates, tallates, phosphates, benzoin ethers, and trimellitates. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 2 wt%, at least about 4 wt%, at least about 6 wt%, or at least about 8 wt%) and/or at most about 10 wt% (e.g., at most about 9 wt%, at most about 7 wt%, at most about 5 wt%, or at most about 3 wt%) of the plasticizer.
  • In some embodiments, the ink composition described herein can optionally include one or more antioxidants. In general, an antioxidant can inhibit oxidation (e.g., thermally induced oxidation) of the ink composition (e.g., when the ink composition is in a hot molten state during jetting). Examples of antioxidants include butylated hydroxyanisole (BHA); butylated hydoxytoluene (BHT); propyl gallate; tert-butyl hydroquinone (TBHQ); ethyl enedi ami netetraacetic acid (EDTA); methyl paraben; and propyl paraben. Commercial examples of the antioxidants include Irganox 1010 (i.e., a hindered phenol) and Irgafos 168 (i.e., tris(2,4-di-tert-butylphenyl)phosphite) available from BASF Corporation (Florham Park, NJ). In some embodiments, the ink composition contains at least about 0.1 wt% (e.g., at least about 0.5 wt%, at least about 1 wt%, or at least about 3 wt%) and at most about 5 wt% (e.g., at most about 4 wt%, at most about 3 wt%, at most about 2 wt%, or at most about 1 wt%) of the antioxidant.
  • In some embodiments, the ink composition described herein can optionally include one or more dispersants. In general, a dispersant can assist in stabilizing an insoluble component (e.g., a colorant) in the ink composition. For example, the dispersant can prevent agglomeration of a colorant (e.g., a pigment) in the ink composition. Examples of dispersants include Solsperse 13,650, 13,940, 17,000, J910; Byk 108; Tego Dispers 700; UNIQEMA 5543; and EFKA 5244, 5207, 6750; which are all commercially available from Lubrizol; Byk; Evonik; Croda; and BASF, respectively. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 2 wt%, at least about 4 wt%, at least about 6 wt%, or at least about 8 wt%) and at most about 10 wt% (e.g., at most about 9 wt%, at most about 7 wt%, at most about 5 wt%, or at most about 3 wt%) of the dispersant.
  • In general, the ink composition described herein can have any suitable apparent viscosity. In some embodiments, the ink composition can have an apparent viscosity ranging from at least about 1 centiPoise (cP) (e.g., at least about 5 cP, at least about 10 cP, at least about 15 cP, or at least about 20 cP) to at most about 25 cP (e.g., at most about 20 cP, at most about 15 cP, or at most about 10 cP) measured at 20°C and at 73 s-1.
  • In some embodiments, the ink composition described herein can optionally include one or more conductive agents. In some embodiments, the conductive agent can be a salt (e.g., an organic salt or an inorganic salt). For example, the salt can be a quaternary phosphonium salt (e.g., a tetraalkylphosphonium or tetraarylphosphonium salt), a quaternary ammonium salt (e.g., a tetraalkylammonium or tetraarylammonium salt), an imidazolium salt, or an alkali salt (e.g., a Li, Na, K, or Cs salt).
  • In general, the ink composition described herein can have any suitable conductivity. In some embodiments, the ink composition can have a conductivity ranging from at least about 0 µS/cm (e.g., at least about 10 µS/cm, at least about 50 µS/cm, at least about 100 µS/cm, at least about 200 µS/cm, at least about 300 µS/cm, at least about 400 µS/cm at least about 500 µS/cm, or at least about 1000 µS/cm) to at most about 8000 µS/cm (e.g., at most about 7000 µS/cm, at most about 6000 µS/cm, at most about 5000 µS/cm, at most about 4000 µS/cm, at most about 3000 µS/cm, at most about 2000 µS/cm, or at most about 1000 µS/cm). For example, when the ink composition is designed for use in a continuous inkjet printing process, the ink composition can have a suitable conductivity (e.g., 100-8000 µS/cm) to enable the ink composition to be printed in this process. As another example, when the ink composition is designed for use in a thermal inkjet printing process, the ink composition can have zero conductivity since conductivity is not required in this printing process.
  • In some embodiments, the ink composition is substantially free of a certain material. For example, the ink composition can be substantially free of a wax (e.g., a polyethylene wax), a colorant (e.g., a non-polymeric colorant) other than the polymeric dye according to the present invention, a resin (e.g., a non-polymeric resin) other than the polymeric dye according to the present invention, or a conductive agent (e.g., a salt).
  • In some embodiments, the ink composition can be a solution (in which all solutes (e.g., a polymeric dye according to the present invention are dissolved) or a dispersion (which contains dispersed particles).
    • Printing Process and Product
  • In general, the ink composition described herein can be used in any suitable printing process, including a continuous inkjet (CIJ) printing process, a drop-on-demand printing process (e.g., thermal inkjet (TIJ) printing process or a piezo printing process), a hot-melt printing process, a valvejet printing process, a flexographic printing process, a lithographic printing process, a gravure printing process, a screen printing process, or a pad printing process, or an offset printing process. In some embodiments, the ink composition can be used in a printing process that includes ejecting the ink composition (either continuously or on demand) from a printhead in an inkjet printer onto a substrate to form an image.
  • In some embodiments, in a continuous inkjet printing process, a continuous stream of conductive ink droplets can be ejected from one or more nozzles of a printhead of an inkjet printer. The droplets are electrostatically deflected to address several vertical pixels as the substrate moves relative to the nozzles. CIJ inks generally have a suitable conductivity and allows the droplets to be deflected. The process of jetting ink droplets continuously and directing unneeded drops to the gutter allows the CIJ systems to utilize fast evaporating solvents (e.g., those having a relative evaporation rate (RER) greater than 1 as determined by the ASTM method D3359 and relative to n-butyl acetate) without concern for decap (i.e., the ability to remain in the fluid condition in a printhead nozzle opening on exposure to air) and nozzle clogging, as the nozzles are effectively never idle during operation.
  • In some embodiments, in a continuous inkjet printing process, a continuous ink stream ejected from a printhead is deviated by at least one electrode to which a static or sinusoidal high voltage is applied. Most of the ink stream is not printed and is directed to an ink recovery gutter. During printing, segments of the ink stream are sampled asynchronously, deviated differently depending on their length (the length providing a means of varying the distribution of embedded electrical charge per unit length) and directed towards the substrate. These segments, which can be transformed into spherical drops under the effect of the surface tension, are separated from the jet before they are deflected such that their trajectory is different from the ink stream.
  • In some embodiments, in a drop-on-demand printing process, inks can be jetted by either thermal inkjet cartridges or piezo drop-on-demand printheads. To print inks, an ink is loaded into a reservoir where it is either pumped or fed by gravity to a jetting chamber of a cartridge or printhead. In the case of the thermal inkjet cartridge, a liquid ink is ejected from a printhead by being rapidly heated, causing a rapid phase change from liquid to gas, thus causing a rapid volume expansion and subsequently causing a droplet to eject from an orifice. In the case of a piezo-based device, a liquid ink is ejected from a printhead by activation of a piezo transformer (PZT), which causes a pressure wave to be exerted upon the ink and an ink droplet can be ejected from an orifice. Both devices are referred to as drop-on-demand since a droplet of ink is ejected only when a heater or PZT material is activated. Each cartridge or printhead contains an array of several orifices across its width. Activation of each orifice in such an array is performed methodically by the printer such that an image is formed drop-wise on a substrate, which is positioned a short distance from the orifice array. The printers are designed such that an orifice array and a substrate move relative to one another in order to form an image.
  • This disclosure also features a product that includes a substrate and a solid ink defining an image on the substrate, in which the solid ink includes the ink composition described herein. The substrate can be any suitable materials (e.g., porous or non-porous materials), such as films, coated and non-coated papers, plastics, glass, metals, and cardboards. In some embodiments, the substrate can be a package material, such as a cardboard (e.g., a corrugated cardboard) or a film (e.g., a shrink wrap). Examples of suitable substrates include flexible packaging films (e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, or poly(lactic acid) films), rigid plastic materials (e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, poly(lactic acid), polyvinylchloride materials), corrugated cardboard (e.g., bleached, unbleached, and coated cardboard), boxboard (e.g., glossy coated, matte coated, and uncoated boxboards), bottle materials (e.g., glass, polyethylene terephthalate, polyethylene, polypropylene, and poly(lactic acid) materials). The contents of all publications cited herein (e.g., patents, patent application publications, and articles) are hereby incorporated by reference in their entirety.
  • The present invention will be further illustrated below by means of several preparatory examples, which are provided for indicative purposes only and without any limitation of the present invention.
    • EXPERIMENTAL PART Example 1 Synthesis of Disperse Red 1 Methacryloyloxyethylsuccinate
  • The title product is obtained by reacting the Disperse Red 1 with methacryloyloxyethylsuccinic acid according to the following reaction.
    Figure imgb0006
    • EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride
    • DMAP : Dimethylaminopyridine
    • DCM : Dichloromethane
  • In a round bottom flask, Disperse red 1 (10.0 g, 31.9 mmol, 1 eq) and 2-(methacryloyloxy)ethyl succinate (8.1g, 35.0 mmol, 1.1 eq) were dissolved in 310 mL of dichloromethane. The mixture was cooled down to 0°C with an ice bath, then EDC.HCl (7.4 g, 38.5 mmol, 1.2 eq) and DMAP (0.78 g, 6.4 mmol, 0.2 eq) were successively added in small portions under nitrogen flow. At the end of the addition, the mixture was left under stirring at room temperature for 1 hour. At the end of the reaction, 100 mL of HCl 0.5 M were added, and the mixture was transferred in a separatory funnel. After decantation, the organic phase is collected and dried over anhydrous sodium sulfate, filtered on frit Por4, and concentrated under reduced pressure. When dichloromethane was completely removed, the polymerizable blue monomer appears to be a red powder. The chemical structure of this monomer was confirmed by 1H NMR (in Chloroform-d).
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.34 - 8.14 (m, 2H), 7.92 - 7.68 (m, 4H), 6.81 - 6.63 (m, 2H), 6.05 (p, J = 1.1 Hz, 1H), 5.51 (p, J = 1.6 Hz, 1H), 4.26 (d, J = 8.1 Hz, 6H), 3.73 - 3.28 (m, 4H), 2.57 (h, J = 1.6 Hz, 4H), 1.87 (t, J = 1.2 Hz, 3H), 1.18 (t, J = 7.0 Hz, 3H).
    • Example 2 Synthesis of Blue Patent V Methacryloyloxyethylsuccinate
  • The title product is obtained by reacting the Blue Patent V with methacryloyloxyethylsuccinic acid according to the following reaction.
    Figure imgb0007
    • EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride
    • DMAP : Dimethylaminopyridine
    • DCM : Dichloromethane
    • NBu : tetrabutyl ammonium
  • The first step consists in the substitution of the sodium counter-ion with tetrabutyl ammonium to decrease the hydrophilic character of Patent Blue V. In a round bottom flask, Patent blue V sodium salt (20.0 g, 0.034 mol, 1 eq) and Tetra-n-butylammonium bromide (22.1 g, 0.069 mol, 2 eq) were solubilized in 400 mL of a mixture of dichloromethane/water 3/1 v/v. The biphasic mixture was vigorously stirred for 3 hours at room temperature, then 1L of dichloromethane and 400 mL of HCl 0.5M were added before transferring the solution in a separatory funnel. After the two phases have settled, the organic phase was recovered, dried over anhydrous sodium sulfate, filtered on frit Por4 and concentrated under reduced pressure. After the complete removal of dichloromethane, the intermediate product was obtained as a dark violet powder. Its chemical structure was confirmed by 1H NMR (in Chloroform-d).
  • The second step consists in the reaction between the dye and the polymerizable monomer. In a round-bottom flask, the product of the step one (20.9 g, 16.9 mmol, 1 eq) and 2-(methacryloyloxy)ethyl succinate (4.28 g, 18.6 mmol, 1.1 eq) were dissolved in 150 mL of dichloromethane. The mixture was cooled down to 0°C with an ice bath, then EDC.HCl (3.9 g, 20.4 mmol,1.2 eq) and DMAP (0.41 g, 3.4 mmol, 0.2 eq) were successively added in small portions under nitrogen flow. At the end of the addition, the mixture was left under stirring at room temperature for 4 hours. At the end of the reaction, 200 mL of dichloromethane and 150 mL of HCl 0.5M were added, and the mixture was transferred in a separatory funnel. After decantation, the organic phase was dried over anhydrous sodium sulfate, filtered on frit Por4 and concentrated under reduced pressure. When dichloromethane was completely removed, the polymerizable blue monomer appears to be a dark blue powder. The chemical structure of this monomer was confirmed by 1H NMR (in Chloroform-d).
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.65 (s, 1H), 7.45 (dd, J = 9.1, 6.7 Hz, 4H), 6.80 - 6.57 (m, 5H), 6.14 - 5.96 (m, 1H), 5.50 (m, 1H), 4.24 (s, 4H), 3.52 (q, J = 7.1 Hz, 8H), 3.42 - 3.10 (m, 16H), 2.96 (t, J = 6.9 Hz, 2H), 2.75 (t, J = 6.9 Hz, 2H), 1.97 - 1.78 (m, 3H), 1.78 - 1.50 (m, 16H), 1.50 - 1.08 (m, 28H), 0.93 (t, J = 7.3 Hz, 24H).
    • Example 3 Synthesis of solvent violet 13 methacryloyloxyethylsuccinate
  • The title product is obtained by reacting the solvent violet 13 with methacryloyloxyethylsuccinic acid according to the following reaction.
    Figure imgb0008
    • EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride
    • DMAP : Dimethylaminopyridine
    • DCM : Dichloromethane
  • In a round-bottom flask, Solvent Violet 13 (5.0 g, 15.2 mmol, 1 eq) and 2-(methacryloyloxy)ethyl succinate (3.84 g, 16.7 mmol, 1.1 eq) were dissolved in 35 mL of dichloromethane. The mixture was cooled down to 0°C with an ice bath, then EDC.HCl (3.49g, 18.2 mmol, 1.2 eq) and DMAP (0.37 g, 3.04 mmol, 0.2 eq) were successively added in small portions under nitrogen flow. At the end of the addition, the mixture was warmed at 30°C and left under stirring at this temperature for 1 hour. At the end of the reaction, 50 mL of dichloromethane and 50 mL of HCl 0.5 M were added, and the mixture was transferred in a separatory funnel. After decantation, the organic phase was washed with 50 mL of deionized water, then dried over anhydrous sodium sulfate, filtered on frit Por4 and concentrated under reduced pressure. When dichloromethane was completely removed, the color of polymerizable monomer appears to be red-purple. The chemical structure of this monomer was confirmed by 1H NMR (in Chloroform-d).
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 11.55 (s, 1H), 8.42 - 8.07 (m, 2H), 7.88 - 7.59 (m, 2H), 7.43 (d, J = 9.4 Hz, 1H), 7.36 - 7.05 (m, 5H), 6.25 - 6.04 (m, 1H), 5.69 - 5.50 (m, 1H), 4.51 - 4.27 (m, 4H), 3.12 (t, J = 7.0 Hz, 2H), 2.91 (t, J = 7.0 Hz, 2H), 2.40 (s, 3H), 2.02 - 1.87 (m, 3H).
    • Example 4 Synthesis of disperse red 60 methacryloyloxyethylsuccinate
  • The title product is obtained by reacting the disperse red 60 with methacryloyloxyethylsuccinic acid according to the following reaction.
    Figure imgb0009
    • EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride
    • DMAP : Dimethylaminopyridine
    • DCM : Dichloromethane
  • In a round-bottom flask, Disperse Red 60 (10.0 g, 28.4 mmol) and 2-(Methacryloyloxy)ethyl succinate (7.84 g, 34.1 mmol) were dissolved in 40 mL of dichloromethane. The mixture was cooled down to 0°C and deoxygenated under nitrogen flow, then, EDC.HCl (7.60 g, 39.6 mmol) and DMAP (1.74 g, 14.2 mmol) were added. The mixture was then heated to 40°C and left under magnetic stirring for 8h. When the reaction was complete, the mixture was diluted by adding 250 mL of dichloromethane, then successively washed with 100 mL of HCl 1M, 100 mL of NaOH 1M and 100 mL of deionized water. The organic phase was dried over anhydrous sodium sulfate, filtered on frit Por4 and concentrated under vacuum until complete removal of solvent. Disperse red 60 methacryloyloxyethylsuccinate was recovered as a red powder. The chemical structure of this monomer was confirmed by 1H NMR (in Chloroform-d).
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.42 - 8.08 (m, 2H), 7.86 - 7.65 (m, 2H), 7.57 - 7.39 (m, 2H), 7.39 - 7.24 (m, 1H), 7.24 - 7.09 (m, 2H), 6.53 (s, 1H), 6.19 - 6.08 (m, 1H), 5.65 - 5.52 (m, 1H), 4.36 (d, J = 5.0 Hz, 4H), 3.05 (td, J = 7.0, 0.9 Hz, 2H), 2.85 (td, J = 7.0, 0.8 Hz, 2H), 2.02 - 1.86 (m, 3H).
    • Example 5 Synthesis of black polymeric dye
  • Starting from the synthesized monomeric dyes of examples 1 and 2, a black polymeric dyes was obtained by free-radical polymerization according to the following scheme.
    Figure imgb0010
    • AIBN: 2,2'-Azobis(2-methylpropionitrile)
    • DMF: Dimethylformamide
  • In a round-bottom flask, Blue Patent V Methacryloyloxyethylsuccinate (4.0 g, 1.77 mmol), Disperse Red 1 Methacryloyloxyethylsuccinate (1.37 g, 2.53 mmol), ethyl methacrylate (3.6 g, 31.5 mmol) and AIBN (0.12 g, 0.72 mmol) were dissolved in 40 mL of DMF. The mixture was deoxygenated under argon flux for 30 min at room temperature, then the polymerization was performed at 80°C overnight. When the polymerization was completed, DMF was removed by evaporation under vacuum. Next, the product was dissolved in dichloromethane and precipitated twice in a cold mixture of MeOH/Et2O 3/7 v/v then once in pentane. After drying in an oven at 40°C, the polymer was obtained as a black powder. The chemical structure of synthesized polymer was confirmed by 1H NMR (in Chloroform-d), while the molecular weight was evaluated by GPC with DMF as eluent and PMMA as standard (Mw=60,000 Da). The polymeric dye showed a IWS value of 2, evaluated as described in the ISO 12040 standard.
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.70 (s, 1Hx), 8.34 (d, J = 8.6 Hz, 2Hz), 7.92 (t, J = 8.4 Hz, 4Hz), 7.51 (d, J = 9.1 Hz, 4Hx), 6.90 - 6.60 (m, 5Hx + 2Hz), 4.54 - 3.83 (m, 4Hx + 2Hy + 6Hz), 3.71 (s, 2Hz), 3.65 - 3.44 (m, 8Hx + 2Hz), 3.34 (d, J = 8.6 Hz, 16Hx), 3.05 (s, 2Hx), 2.82 (s, 2Hx), 2.68 (s, 4Hz), 2.39 - 1.58 (m, 18Hx + 2Hy + 5Hz), 1.56 - 1.15 (m, 28Hx + 3 Hy + 3Hz), 1.15 - 0.48 (m, 27Hx + 3Hy + 3Hz).
    • Example 6 Synthesis of red polymeric dye
  • Starting from the synthesized monomeric dyes of examples 1 and 3, a red polymeric dye was obtained by free-radical polymerization according to the following scheme.
    Figure imgb0011
    • AIBN: 2,2'-Azobis(2-methylpropionitrile)
    • DMF: Dimethylformamide
  • In a round-bottom flask, Solvent violet 13 Methacryloyloxyethylsuccinate (2.0 g, 3.25 mmol), ethyl methacrylate (3.3 g, 28.9 mmol), Disperse red 1 Methacryloyloxyethylsuccinate (1.2 g, 2.27 mmol) and AIBN (114 mg, 0.70 mmol) were dissolved in 27.5 mL of DMF. The mixture was deoxygenated under argon flow for 15 min at room temperature, then the polymerization was performed at 80°C overnight. When the polymerization was completed, DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane then precipitated in hexane. The polymer was let to settle, and the supernatant solvent was removed. After drying in an oven at 40°C, the polymer was obtained as a dark red powder. The chemical structure of synthesized polymer was confirmed by 1H NMR (in Chloroform-d), while the molecular weight was evaluated by GPC with DMF as eluent and PMMA as standard (Mw=55,500 Da). The polymeric dye showed a IWS value of 3, evaluated as described in the ISO 12040 standard.
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 11.46 (s, 1Hx), 8.41 - 7.97 (m, 2Hx + 2Hz), 7.97 - 7.56 (m, 2Hx + 4Hz), 7.37 (d, J = 2.3 Hz, 1Hx), 7.25 - 6.88 (m, 5Hx), 6.73 (d, J = 9.1 Hz, 2Hz), 4.49 - 3.73 (m, 4Hx + 2Hy + 6Hz), 3.73 - 3.28 (m, 4Hz), 3.02 (d, J = 6.8 Hz, 2Hx), 2.82 (s, 2Hx), 2.59 (s, 4Hz), 2.43 - 2.18 (m, 3Hx), 2.17 - 1.54 (m, 2Hx + 5Hy + 2Hz),1.54 - 0.23 (m, 3Hx + 3Hy + 6Hz).
    • Example 7 Synthesis of blue polymer dye
  • Starting from the synthesized monomeric dyes of examples 2 and 3, a blue polymeric dye was obtained by free-radical polymerization according to the following scheme.
    Figure imgb0012
    • AIBN: 2,2'-Azobis(2-methylpropionitrile)
    • DMF: Dimethylformamide
  • In a round-bottom flask, Patent Blue V Methacryloyloxyethylsuccinate (3.0 g, 1.48 mmol), Solvent Violet 13 Methacryloyloxyethylsuccinate (1.4 g, 2.11 mmol), ethyl methacrylate (3.0 g, 26.4 mmol) and AIBN (98 mg, 0.60 mmol) were dissolved in 32 mL of DMF. The mixture was deoxygenated under argon flux for 30 min at room temperature, then the polymerization was performed at 80°C overnight. When the polymerization was complete, DMF was removed by evaporation under vacuum. Next, the product was dissolved in dichloromethane and precipitated twice in a mixture of Methanol / Diethyl ether 2:8 v/v then once in diethyl ether. After drying in an oven at 50°C, the polymer was obtained as a dark blue powder. The chemical structure was confirmed by 1H NMR (in Chloroform-d), while the molecular weight was evaluated by GPC with DMF as eluent and PMMA as standard (Mw = 87,000 Da).
  • 1H NMR(300 MHz, Chloroform-d) δ (ppm) 11.54 (s, 1Hz), 8.69 (s, 1Hx), 8.42 - 8.07 (d, J = 8.7 Hz, 2Hz), 7.89 - 7.65 (d, J = 7.4 Hz, 2Hz), 7.62 - 7.35 (m, 4Hx), 7.32 - 7.01 (m, 5Hz), 6.88 - 6.57 (m, 5Hx), 4.56 - 3.84 (m, 4Hx + 2Hy + 4 Hz), 3.69 - 3.42 (m, 8Hx), 3.33 (m, 16Hx), 3.10 (m, 4Hx), 2.99 - 2.52 (m, 4Hz), 2.38 (s, 3Hz), 2.33 - 1.57 (m, 18Hx + 2Hy + 2Hz), 1.57 - 1.16 (m, 19Hx + 3Hy + 3Hz), 1.16 - 0.32 (m, 36Hx + 3Hy).
    • Example 8 Synthesis of green polymer dye
  • Starting from the synthesized monomeric dyes of examples 2 and 4, a red polymeric dye was obtained by free-radical polymerization according to the following scheme.
    Figure imgb0013
    • AIBN: 2,2'-Azobis(2-methylpropionitrile)
    • DMF: Dimethylformamide
  • In a round-bottom flask, Patent Blue V Methacryloyloxyethylsuccinate (1.0 g, 0.495 mmol), Disperse Red 60 Methacryloyloxyethylsuccinate (2.3 g, 3.8 mmol), ethyl methacrylate (2.7 g, 23.8 mmol) and AIBN (92 mg, 0.56 mmol) were dissolved in 26 mL of DMF. The mixture was deoxygenated under argon flux for 30 min at room temperature, then the polymerization was performed at 80°C overnight. When the polymerization was complete, DMF was removed by evaporation under vacuum. Next, the product was dissolved in dichloromethane and precipitated twice in a mixture of Methanol / Diethyl ether 2:8 v/v then once in diethyl ether. After drying in an oven at 50°C, the polymer was obtained as a dark green powder. The chemical structure was confirmed by 1H NMR (in Chloroform-d), while the molecular weight was evaluated by GPC with DMF as eluent and PMMA as standard (Mw = 73,000 Da).
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.68 (s, 1Hx), 8.26 (s, 1Hz), 8.15 (s, 1Hz), 7.72 (s, 2Hz), 7.47 (m, 4Hx + 2Hz), 7.28 (s, 1Hz), 7.15 (d, J = 7.5 Hz, 2Hz), 6.86 - 6.62 (m, 5Hx), 6.52 (s, 1Hz), 4.70 - 3.77 (m, 4Hx + 2Hy + 4Hz), 3.69 - 3.42 (m, 8Hx), 3.39 - 3.18 (m, 16Hx), 3.18 - 2.93 (m, 2Hx + 2Hz), 2.93 - 2.56 (m, 2Hx + 2Hz), 2.16 - 0.53.
    • Example 9 Inkjet ink formulation
  • An inkjet ink has been prepared by dissolving different amount of the black polymeric dye of example 5 in methyl ethyl ketone (MEK). A coating was done on white sealed cardboard (opacity cards of Leneta supplier) using a wet film deposit of 12 µm and a standard coating speed of 15m/min. The following table 1 summarizes the lightness (L*) evaluated on coating and the viscosity (cP) of the resulting ink at the several weight percentages. TABLE 1
    %wt Lightness (L*) viscosity (cP)
    6.0 31 1.1
    7.5 24 1.2
    8.0 20 1.4
    10.0 16 2.1
    12.5 10 3.3
    15 5 5.4
    17.5 3 -
    • Example 10 Printing test
  • An inkjet ink has been prepared by dissolving a conductive agent (1%wt) and the black polymeric dye of example 5 (12,5%wt) in MEK.
  • After printing on cardboard the visual aspect was dark black color as illustrated in Figure 1.
  • The light fastness resistance was visually evaluated by comparing pictures taken at different times of storage in a sun test apparatus at an irradiance of 60 ± 2 W/m2 and a temperature of 65 ± 3°C as described in the ISO 16474-2 standard. The results are illustrated in Figures 2-6.
  • In actual indoor conditions, the results illustrated in figures 2-6 correspond to a decrease of 30% of the color strength of the printed sample after at least two years.
    • EXAMPLE 11
  • An inkjet ink according to the present invention (INK1) has been prepared by dissolving the black polymeric dye of example 5 at 15% by weight in methyl ethyl ketone (MEK). Two reference inkjet inks have been prepared by dissolving the commercial Solvent Black27 (INK2) and Solvent Black 27 (INK3) dyes at 6% by weight and a polymeric resin at 9% by weight in MEK. The polymeric resin is a solution of nitrocellulose in isopropyl alcohol with a ratio nitrocellulose to isopropyl alcohol equal to 70:30.
  • Three different coatings were done on white sealed cardboard (opacity cards of Leneta supplier) using a wet film deposit of 12 µm and a standard coating speed of 15m/min.
  • The inks were compared for compliance to regulation and viscosity, while the coatings were compared for lightness and visual aspect. The results are summarized in the following table 3. TABLE 3
    Compliance Viscosity (cP) Lightness (L*) Visual Aspect
    INK1 OK 5.6 5 Full black
    INK2 KO 4.9 6 Full black
    INK3 KO 4.7 6 Full black
    OK : conform to REACh regulation
    KO : CMR or dangerous for aquatic life
  • The data of viscosity, lightness and visual aspect confirmed the good results for INK1 of the present invention, fully comparable to reference INK2 and INK3, with the advantage of satisfying the requirements of REACh regulation.
    • TEST METHODS VISCOSITY
  • Shear viscosity was measured by using a shear rate of 73 s-1 at 20°C as described in standard DIN 53019-1 (e.g., by using a viscometer with coaxial cylinders of the "Couette" type).
    • LIGHTNESS
  • Lightness (L*) measurements were done with a CIELAB (or CIE L*a*b*) spectrophotometer (e.g., an X- Rite eXact instrument). The CIELAB space is defined in three dimensions where L* is related to the lightness, a* is the red/green color parameter and b* is the yellow/blue color parameter.
  • The synthesis of two additional black polymeric dyes having different molecular weight is illustrated in the following example 12 and 13.
    • EXAMPLE 12
  • Starting from the synthesized monomeric dyes of examples 1 and 2, a black polymeric dye was obtained by free-radical polymerization according to the following scheme.
    Figure imgb0014
    • AIBN: 2,2'-Azobis(2-methylpropionitrile)
    • DMF: Dimethylformamide
  • In a round-bottom flask, Patent Blue V Methacryloyloxyethylsuccinate, ethyl methacrylate, Disperse Red 1 Methacryloyloxyethylsuccinate, dodecanthiol and AIBN (2 mol% to monomers) were dissolved in DMF (dry extract 20 wt%). The mixture was deoxygenated under argon flow for 15 min at room temperature, then the polymerization was performed at 70°C. After reaching a conversion of about 80%, portions of AIBN were added to increase the conversion higher than 95 %. When the polymerization was completed, DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane then precipitated once in diethyl ether, then twice in a methanol/diethyl ether mixture. The polymer was let to settle, and the supernatant solvent was removed. After drying in an oven at 50°C, the polymer was obtained as a black powder. The chemical structure of synthesized polymer was confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC (Mw = 14,900 Da). The polymeric dye showed a IWS value of 2, evaluated as described in the ISO 12040 standard.
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.64 (s, 1Hx), 8.30 (d, J = 8.6 Hz, 2Hz), 7.85 (t, J = 8.4 Hz, 4Hz), 7.46 (d, J = 9.1 Hz, 4Hx), 6.90 - 6.60 (m, 5Hx + 2Hz), 4.54 - 3.83 (m, 4Hx + 2Hy + 6Hz), 3.71 (s, 2Hz), 3.65 - 3.44 (m, 8Hx + 2Hz), 3.34 (d, J = 8.6 Hz, 16Hx), 3.05 (s, 2Hx), 2.82 (s, 2Hx), 2.68 (s, 4Hz), 2.39 - 1.58 (m, 18Hx + 2Hy + 5Hz), 1.56 - 1.15 (m, 28Hx + 3 Hy + 3Hz), 1.15 - 0.45 (m, 27Hx + 3Hy + 3Hz).
    • EXAMPLE 13
  • Starting from the synthesized monomeric dyes of examples 1 and 2, a black polymeric dye was obtained by free-radical polymerization according to the following scheme.
    Figure imgb0015
    • AIBN: 2,2'-Azobis(2-methylpropionitrile)
    • DMF: Dimethylformamide
  • In a round-bottom flask, Patent Blue V Methacryloyloxyethylsuccinate (2.0 g, 1.27 mmol), Disperse Red 1 Methacryloyloxyethylsuccinate (1.37 g, 2.54 mmol), butyl methacrylate (5.49 g, 38.6 mmol) and AIBN (70.0 mg, 0.42 mmol) were dissolved in 37 mL of DMF. The mixture was deoxygenated under argon flux for 15 min at room temperature, then the polymerization was performed at 70°C overnight. When the polymerization was completed, DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane then precipitated in pentane. The polymer was then let to settle, and the supernatant solvent was removed. After drying in an oven at 40°C, the polymer was obtained as a black powder. The chemical structure of synthesized polymer was confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC (Mw=75,000 Da).
  • 1H NMR (300 MHz, Chloroform-d) δ (ppm) 8.67 (s, 1Hx), 8.30 (d, J = 8.8 Hz, 2Hz), 7.89 (t, J = 8.1 Hz, 4Hz), 7.48 (dd, J = 9.4, 6.9 Hz, 4Hx), 6.88 - 6.58 (m, 5Hx + 2Hz), 4.40 - 4.03 (m, 4Hx + 6Hz), 4.03 - 3.76 (m, 2Hy), 3.68 (t, J = 6.5 Hz, 2Hz), 3.52 (q, J = 7.0 Hz, 8Hx + 2Hz), 3.32 (dd, J = 11.0, 5.6 Hz, 16Hx), 3.09 - 2.48 (m, 4Hx + 4Hz), 2.30 - 0.49 (m, 73Hx + 12 Hy + 8 Hz).
  • It is understood that, given the above description of the embodiments of the invention, various modifications may be made by one skilled in the art. Such modifications are intended to be encompassed by the claims below.

Claims (18)

  1. A polymeric dye comprising monomer repeating units having the following formulas (I) and (II):
    Figure imgb0016
     wherein M1 and M2, equal or different each other, are reactive monomers, and C1 and C2, different each other, are chromophore units.
  2. The polymeric dye according to claim 1, further comprising a monomer repeating unit having the following formula (III):
    Figure imgb0017
     wherein M3 is a reactive monomer, and C3 is a chromophore unit different from C1 and C2.
  3. The polymeric dye according to claim 1 or 2, further comprising a monomer repeating unit having the following formula (IV):
    Figure imgb0018
     wherein M4 is a reactive monomer.
  4. The polymeric dye according to any one of claims 1 to 3, further comprising a monomer repeating unit having the following formula (V):
    Figure imgb0019
     wherein M5 is a reactive monomer, and C4 is a chromophore unit different from C1-C3.
  5. The polymeric dye according to any one of claims 1 to 4, wherein M1 to M5, equal or different each other, are selected from the group consisting of acrylic acid monomer, methacrylic acid monomer, acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, vinyl alcohol monomer, and vinyl amine monomer.
  6. The polymeric dye according to claim 1, wherein any one of C1-C4 can be a blue chromophore unit derived from a commercial dye selected from the group consisting of:
    Acid Blue 1, 3, 7, 9, 15, 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 52, 57, 58, 61:1, 62, 62:1, 63, 64, 65, 68, 69, 72, 74, 78, 78:1, 79, 80, 81, 81:1, 83, 90, 92, 96, 103, 104, 111, 112, 113, 114, 120, 124, 127, 127:1, 128, 129, 129:1, 138, 138:1, 140, 142, 145, 150, 156, 158, 171, 175, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 215, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 277, 277:1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 344, 350;
    Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29;
    Direct Blue 1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98,106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218, 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291;
    Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 77, 79, 79:1, 79:2, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 281, 284, 285, 287, 288, 291, 291:1, 293, 295, 297, 301, 315, 330, 333, 373;
    Food Blue 1, 2;
    Reactive Blue 2, 3, 4, 5, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79, 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194, 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236;
    Solvent Blue 4, 5, 6, 35, 38, 48, 59, 67, 70, 104, and 136.
  7. The polymeric dye according to claim 1, wherein any one of C1-C4 can be a red chromophore unit derived from a commercial dye selected from the group consisting of:
    Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97:1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 143:1, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415, 447;
    Basic Red 1, 2, 9, 12, 13, 37;
    Direct Red 2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243, 254;
    Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328, 337, 343;
    Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105, 106;
    Reactive Red 2, 3, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78, 83, 84, 106, 111, 312, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180,183, 184, 187, 190, 193, 194, 195, 198, 218, 220, 222, 223, 228, 235;
    Solvent Red 1, 23, 29, 49, 119, 122, 125, 127, 130, 132, 135, 149, 160, 164, 168, 169, 172 and 233.
  8. The polymeric dye according to claim 1, wherein any one of C1-C4 can be a green chromophore unit derived from a commercial dye selected from the group consisting of:
    Acid Green 1, 3, 5, 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 50, 56, 73, 81, 84, 104, 108, 109;
    Basic Green 1, 4, 5;
    Direct Green 26, 28, 59, 80, 85;
    Disperse Green 9;
    Food Green 2, 3;
    Reactive Green 5, 7, 8, 12, 15, 19, 21;
    Solvent Green 1, 3, 7, and 11.
  9. The polymeric dye according to claim 1, wherein any one of C1-C4 can be a chromophore unit derived from a commercial dye selected from the group consisting of:
    Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40:1, 42, 44, 49, 59, 59:1, 61, 65, 72, 73, 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219:1, 220, 230, 232, 235, 241, 242, 246;
    Basic Yellow 1, 2, 11, 12, 14, 21, 28, 32, 36, 57, 87;
    Direct Yellow 4, 7, 8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 59, 62, 79, 86, 87, 98, 105, 106, 130, 132, 137, 142, 147, 153;
    Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227, 231, 232;
    Food Yellow 3, 4, 5;
    Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102, 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176;
    Solvent Yellow 2, 3, 7, 10, 13, 14, 19, 25, 28, 33, 88, 89, 114, 146, 163;
    Acid Orange 3, 6, 7, 8, 10, 12, 19, 20, 24, 51, 56, 63, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, 144, 149, 152, 156, 162, 166, 168;
    Basic Orange 2, 14, 15, 21, 22, 31, 69;
    Direct Orange 6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118;
    Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142;
    Reactive Orange 1, 4, 5, 7, 11, 2, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92, 93, 95, 107;
    Solvent Orange 1, 2, 3, 7, 11, 15, 20, 25, 54, 60, 62, 63, 86, 99, 105;
    Acid Violet 7, 9, 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126;
    Basic Violet 1, 2, 3, 4, 7, 10, 14;
    Direct Violet 9, 35, 51, 66, 94, 95;
    Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77;
    Food Violet 2;
    Reactive Violet 1, 2, 4, 5, 6, 8, 9, 22, 23, 33, 36, 38;
    Solvent Violet 8, 9, 11, 13, 14, and 38.
  10. The polymeric dye according to claim 1, wherein said polymeric dye has a high solubility in an organic solvent at 25°C.
  11. A method for synthetizing a polymeric dye comprising the steps of:
    (1) reacting a dye comprising a first reactive function with a polymerizable monomer comprising a second reactive function to get a polymerizable monomer dye having any one of the following formulas (I) to (III) and (V):
    Figure imgb0020
     wherein M1, M2, M3, and M5, equal or different each other, are reactive monomers, and C1 to C4, different each other, are chromophore units,
    (2) copolymerizing at least one polymerizable monomer dye (I) to (III) and (V) with a polymerizable monomer having the following formula (IV)
    Figure imgb0021
     wherein M4 is a reactive monomer, and
    (3) recovering the resulting polymeric dye.
  12. The method for synthetizing a polymeric dye according to claim 11, wherein said first reactive function is selected from the group consisting of a hydroxyl group, an amine group, or a carboxyl group.
  13. The method for synthetizing a polymeric dye according to claim 11, wherein said second reactive function is selected from the group consisting of a carboxylic group, an acyl chloride, an anhydride group, an ester group, a hydroxyl group, or an amine group.
  14. The method for synthetizing a polymeric dye according to claim 11, wherein M1 to M5, equal or different each other, are selected from the group consisting of acrylic acid monomer, methacrylic acid monomer, acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, vinyl alcohol monomer, and vinyl amine monomer.
  15. An ink composition comprising a polymeric dye as defined in any one of claims 1 to 10, wherein said composition is a liquid composition, a dispersion composition, an emulsion composition, or a solid composition.
  16. The ink composition according to claim 15, wherein said ink composition is a liquid composition comprising said polymeric dye and an organic solvent, and wherein said polymeric dye is in an amount of from 1% to 70%, preferably from 3% to 50%, by weight said ink composition.
  17. The ink composition according to claim 15, wherein said ink composition is a solid composition comprising said polymeric dye and a fusible carrier, and wherein said polymeric dye is in an amount of from 1% to 70%, preferably from 3% to 50%, by weight said ink composition.
  18. A polymeric dye comprising :
    • at least one monomer repeating unit having the following formula (I) to (III) and (V):
    Figure imgb0022
     wherein M1, M2, M3, and M5, equal or different each other, are reactive monomers, and C1 to C4, different each other, are chromophore units, and
    • a monomer repeating unit having the following formula (IV):
    Figure imgb0023
    wherein M4 is a reactive monomer, and
    wherein said polymeric dye is soluble in organic solvent, preferably having a solubility in an organic solvent at 25°C of at least 1 wt%, and insoluble in water, preferably having a solubility in water at 25°C of less than 0.1 wt%.
EP23158134.9A 2023-02-23 2023-02-23 Polymeric dyes Withdrawn EP4421131A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP23158134.9A EP4421131A1 (en) 2023-02-23 2023-02-23 Polymeric dyes
AU2024225279A AU2024225279A1 (en) 2023-02-23 2024-02-23 Polymeric dyes
PCT/EP2024/054622 WO2024175761A1 (en) 2023-02-23 2024-02-23 Polymeric dyes
EP24706454.6A EP4669709A1 (en) 2023-02-23 2024-02-23 Polymeric dyes
KR1020257027987A KR20250151639A (en) 2023-02-23 2024-02-23 polymer dyes
JP2025549579A JP2026507071A (en) 2023-02-23 2024-02-23 polymer dyes
CN202480014588.8A CN120917101A (en) 2023-02-23 2024-02-23 Polymeric dyes
MX2025009889A MX2025009889A (en) 2023-02-23 2025-08-21 Polymeric dyes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP23158134.9A EP4421131A1 (en) 2023-02-23 2023-02-23 Polymeric dyes

Publications (1)

Publication Number Publication Date
EP4421131A1 true EP4421131A1 (en) 2024-08-28

Family

ID=85381190

Family Applications (2)

Application Number Title Priority Date Filing Date
EP23158134.9A Withdrawn EP4421131A1 (en) 2023-02-23 2023-02-23 Polymeric dyes
EP24706454.6A Pending EP4669709A1 (en) 2023-02-23 2024-02-23 Polymeric dyes

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP24706454.6A Pending EP4669709A1 (en) 2023-02-23 2024-02-23 Polymeric dyes

Country Status (7)

Country Link
EP (2) EP4421131A1 (en)
JP (1) JP2026507071A (en)
KR (1) KR20250151639A (en)
CN (1) CN120917101A (en)
AU (1) AU2024225279A1 (en)
MX (1) MX2025009889A (en)
WO (1) WO2024175761A1 (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19651689A1 (en) 1996-12-12 1998-06-18 Agfa Gevaert Ag Inks for ink-jet printing
WO1999061533A1 (en) 1998-05-28 1999-12-02 Marconi Data Systems, Inc. An ink suitable for ink jet printing
EP1256602A1 (en) * 2001-05-08 2002-11-13 Rolic AG Dichroic mixture
WO2003089533A1 (en) 2002-04-19 2003-10-30 Ppg Industries Ohio, Inc. Water resistant ink jet recordable substrate
US7273897B2 (en) 2001-07-31 2007-09-25 Eastman Kodak Company Ink jet ink composition
WO2007131336A1 (en) * 2006-05-17 2007-11-22 American Dye Source Inc. New materials for lithographic plates coatings, lithographic plates and coatings containing same, methods of preparation and use
US7732509B2 (en) 2006-08-24 2010-06-08 Eastman Kodak Company Polymeric colorant-based ink compositions
CN101787222A (en) 2010-01-08 2010-07-28 武汉科技学院 Method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling
US20100215944A1 (en) * 2007-07-31 2010-08-26 Nguyen My T Polymeric dyes, overcoat compositions and thermal lithographic printing plates
EP2308932A1 (en) * 2008-06-27 2011-04-13 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Method for producing dye polymer, dye polymer and use of the same
CN108071023A (en) 2016-11-08 2018-05-25 绍兴市海印数码科技有限公司 A kind of living polymer dye ink and its applied to the ink-jet printed dyeing and printing process on cotton fabric

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19651689A1 (en) 1996-12-12 1998-06-18 Agfa Gevaert Ag Inks for ink-jet printing
WO1999061533A1 (en) 1998-05-28 1999-12-02 Marconi Data Systems, Inc. An ink suitable for ink jet printing
EP1256602A1 (en) * 2001-05-08 2002-11-13 Rolic AG Dichroic mixture
US7273897B2 (en) 2001-07-31 2007-09-25 Eastman Kodak Company Ink jet ink composition
WO2003089533A1 (en) 2002-04-19 2003-10-30 Ppg Industries Ohio, Inc. Water resistant ink jet recordable substrate
WO2007131336A1 (en) * 2006-05-17 2007-11-22 American Dye Source Inc. New materials for lithographic plates coatings, lithographic plates and coatings containing same, methods of preparation and use
US7732509B2 (en) 2006-08-24 2010-06-08 Eastman Kodak Company Polymeric colorant-based ink compositions
US20100215944A1 (en) * 2007-07-31 2010-08-26 Nguyen My T Polymeric dyes, overcoat compositions and thermal lithographic printing plates
EP2308932A1 (en) * 2008-06-27 2011-04-13 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Method for producing dye polymer, dye polymer and use of the same
CN101787222A (en) 2010-01-08 2010-07-28 武汉科技学院 Method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling
CN108071023A (en) 2016-11-08 2018-05-25 绍兴市海印数码科技有限公司 A kind of living polymer dye ink and its applied to the ink-jet printed dyeing and printing process on cotton fabric

Also Published As

Publication number Publication date
WO2024175761A1 (en) 2024-08-29
JP2026507071A (en) 2026-02-27
EP4669709A1 (en) 2025-12-31
MX2025009889A (en) 2026-02-03
KR20250151639A (en) 2025-10-21
CN120917101A (en) 2025-11-07
AU2024225279A1 (en) 2025-09-04

Similar Documents

Publication Publication Date Title
JP2635266B2 (en) Water-based pigmented ink for inkjet printers
US5169436A (en) Sulfur-containing penetrants for ink jet inks
US5854331A (en) Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks
US5529616A (en) Ink jet inks containing mixtures of alcohols
JP5748995B2 (en) Non-aqueous inkjet ink and ink set
EP0604822A2 (en) Ink jet inks
JP3993968B2 (en) Ink for inkjet printing containing a polymer chromophore modified by ester
EP4077554B1 (en) Aqueous dispersion of polymeric capsules
EP1697470B1 (en) A process for preparing modified particulate solid materials and inks comprising the same
EP4421131A1 (en) Polymeric dyes
US20130065996A1 (en) Pigment Particles Containing a Vinyl Group and Encapsulated by a Cross-linked Polymer
EP4538329A1 (en) Method for synthetizing polymeric dyes
EP4700091A1 (en) Method for synthetizing polymeric dyes
WO2024070862A1 (en) Phthalocyanine pigment, phthalocyanine compound, coloring composition, method for producing phthalocyanine pigment, and method for producing coloring composition
EP1846522A1 (en) Stable pigment dispersions comprising a block copolymer consisting of ionic aromatic monomers
EP4127084B1 (en) Method for preparing pyrrole polymers
JP5920991B2 (en) Ink composition for inkjet printing for polyvinyl chloride substrate
US20240110075A1 (en) Ink Compositions
US12365807B2 (en) Polymeric dispersant
JP2003221521A (en) Colored fine particle dispersion, ink and ink jet recording method using the same
US20120053289A1 (en) Pigment particles encapsulated by a polymer containing at least one vinyl group
JP4365198B2 (en) Aqueous colorant resin composition, process for producing the same, fine particle water-insoluble dye dispersion, and ink for inkjet printer
KR20050038860A (en) Metal complex colorant coordinated with lightfast moiety and liquid composition comprising the same

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20250301